Heterogeneous Ziegler-Natta Catalysts with Fluorided Silica-Coated Alumina

ABSTRACT

Catalyst systems containing a Ziegler-Natta catalyst component are disclosed. Such catalyst systems can contain a co-catalyst and a supported catalyst containing a fluorided silica-coated alumina, a magnesium compound, and vanadium and/or tetravalent titanium.

BACKGROUND OF THE INVENTION

Polyolefins such as high density polyethylene (HDPE) homopolymer andlinear low density polyethylene (LLDPE) copolymer can be produced usingvarious combinations of catalyst systems and polymerization processes.In some end-use applications, it can be beneficial to use a catalystsystem having a supported Ziegler-type catalyst component to producepolymers having broad molecular weight distributions (MWD's) and flat oruniform short chain branch distributions (SCBD's). Accordingly, it is tothese ends that the present invention is directed.

SUMMARY OF THE INVENTION

This summary is provided to introduce a selection of concepts in asimplified form that are further described below in the detaileddescription. This summary is not intended to identify required oressential features of the claimed subject matter. Nor is this summaryintended to be used to limit the scope of the claimed subject matter.

The present invention generally relates to new catalyst compositions,methods for preparing catalyst compositions, methods for using thecatalyst compositions to polymerize olefins, the polymer resins producedusing such catalyst compositions, and articles produced using thesepolymer resins. In particular, aspects of the present invention aredirected to catalyst compositions containing a supported Ziegler-Nattacatalyst component. One such catalyst composition can comprise (1) asupported catalyst comprising a fluorided silica-coated alumina, amagnesium compound, and titanium (IV) and/or vanadium; and (2) aco-catalyst. In some aspects, the co-catalyst can comprise anorganoaluminum compound. These catalyst compositions can be used toproduce, for example, ethylene-based homopolymers and copolymers forvariety of end-use applications.

Processes for producing the catalyst composition also are describedherein. For example, the process can comprise (i) contacting (a) afluorided silica-coated alumina, (b) a magnesium compound, and (c) afirst titanium (IV) compound and/or vanadium compound to form a firstsolid precatalyst, (ii) contacting the first solid precatalyst with anorganoaluminum compound to form a second solid precatalyst, (iii)contacting the second solid precatalyst with a second titanium (IV)compound and/or vanadium compound to form a supported catalyst, and (iv)contacting the supported catalyst with a co-catalyst to form thecatalyst composition.

The present invention also contemplates and encompasses olefinpolymerization processes. Such processes can comprise contacting acatalyst composition with an olefin monomer and optionally an olefincomonomer under polymerization conditions to produce an olefin polymer.Generally, the catalyst composition employed can comprise any of thesupported catalysts (containing a fluorided silica-coated alumina, amagnesium compound, and titanium (IV) and/or vanadium) and any of theco-catalysts disclosed herein.

Polymers produced from the polymerization of olefins, resulting inhomopolymers, copolymers, terpolymers, etc., can be used to producevarious articles of manufacture. A representative and non-limitingexample of an olefin polymer (e.g., an ethylene homopolymer orcopolymer) consistent with aspects of this invention can becharacterized as having the following properties: a melt index of lessthan or equal to about 5 g/10 min (or less than or equal to about 2.5g/10 min), a ratio of Mw/Mn in a range from about 3 to about 5.5 (orfrom about 3.5 to about 4.5), a density in a range from about 0.90 g/cm³to about 0.96 g/cm³ (or from about 0.91 g/cm³ to about 0.945 g/cm³), anda NDR in a range from about 400 to about 600% (or from about 425 toabout 550%). These polymers, in further aspects, can be characterized bylow levels of long chain branches (LCB), and/or by a substantiallyconstant short chain branch distribution (SCBD).

Both the foregoing summary and the following detailed descriptionprovide examples and are explanatory only. Accordingly, the foregoingsummary and the following detailed description should not be consideredto be restrictive. Further, features or variations may be provided inaddition to those set forth herein. For example, certain aspects andembodiments may be directed to various feature combinations andsub-combinations described in the detailed description.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 presents a plot of the molecular weight distributions of thepolymers of Examples 1 and 4-6.

FIG. 2 presents a plot of the molecular weight distributions of thepolymers of Examples 7-8 and 10-11.

FIG. 3 presents a plot of the molecular weight distribution and shortchain branch distribution (SCBD) of the polymer of Example 10.

FIG. 4 presents a plot of the molecular weight distributions and shortchain branch distributions (SCBD's) of the polymers of Examples 10 and13.

FIG. 5 presents a rheology plot (viscosity versus shear rate) at 190° C.for the polymers of Examples 1 and 4-6.

FIG. 6 presents a rheology plot (viscosity versus shear rate) at 190° C.for the polymers of Examples 7-8 and 10-11.

DEFINITIONS

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2nd Ed (1997), can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

While compositions and methods are described herein in terms of“comprising” various components or steps, the compositions and methodscan also “consist essentially of” or “consist of” the various componentsor steps, unless stated otherwise. For example, a supported catalystconsistent with aspects of the present invention can comprise;alternatively, can consist essentially of; or alternatively, can consistof; (i) a fluorided silica-coated alumina, (ii) a magnesium compound,and (iii) titanium (IV) and/or vanadium.

The terms “a,” “an,” “the,” etc., are intended to include pluralalternatives, e.g., at least one, unless otherwise specified. Forinstance, the disclosure of “a co-catalyst” or “a magnesium compound” ismeant to encompass one, or mixtures or combinations of more than one,co-catalyst or magnesium compound, respectively, unless otherwisespecified.

Generally, groups of elements are indicated using the numbering schemeindicated in the version of the periodic table of elements published inChemical and Engineering News, 63(5), 27, 1985. In some instances, agroup of elements can be indicated using a common name assigned to thegroup; for example, alkali metals for Group 1 elements, alkaline earthmetals for Group 2 elements, transition metals for Group 3-12 elements,and halogens or halides for Group 17 elements.

For any particular compound disclosed herein, the general structure orname presented is also intended to encompass all structural isomers,conformational isomers, and stereoisomers that can arise from aparticular set of substituents, unless indicated otherwise. Thus, ageneral reference to a compound includes all structural isomers unlessexplicitly indicated otherwise; e.g., a general reference to pentaneincludes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, while ageneral reference to a butyl group includes an n-butyl group, asec-butyl group, an iso-butyl group, and a tert-butyl group.Additionally, the reference to a general structure or name encompassesall enantiomers, diastereomers, and other optical isomers whether inenantiomeric or racemic forms, as well as mixtures of stereoisomers, asthe context permits or requires. For any particular formula or name thatis presented, any general formula or name presented also encompasses allconformational isomers, regioisomers, and stereoisomers that can arisefrom a particular set of substituents.

The term “substituted” when used to describe a group, for example, whenreferring to a substituted analog of a particular group, is intended todescribe any non-hydrogen moiety that formally replaces a hydrogen inthat group, and is intended to be non-limiting. A group or groups canalso be referred to herein as “unsubstituted” or by equivalent termssuch as “non-substituted,” which refers to the original group in which anon-hydrogen moiety does not replace a hydrogen within that group.Unless otherwise specified, “substituted” is intended to be non-limitingand include inorganic substituents or organic substituents as understoodby one of ordinary skill in the art.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen. Otheridentifiers can be utilized to indicate the presence of particulargroups in the hydrocarbon (e.g., halogenated hydrocarbon indicates thepresence of one or more halogen atoms replacing an equivalent number ofhydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” is usedherein in accordance with the definition specified by IUPAC: a univalentgroup formed by removing a hydrogen atom from a hydrocarbon (that is, agroup containing only carbon and hydrogen). Non-limiting examples ofhydrocarbyl groups include alkyl, alkenyl, aryl, and aralkyl groups,amongst other groups.

The term “polymer” is used herein generically to include olefinhomopolymers, copolymers, terpolymers, and so forth. A copolymer isderived from an olefin monomer and one olefin comonomer, while aterpolymer is derived from an olefin monomer and two olefin comonomers.Accordingly, “polymer” encompasses copolymers, terpolymers, etc.,derived from any olefin monomer and comonomer(s) disclosed herein.Similarly, an ethylene polymer would include ethylene homopolymers,ethylene copolymers, ethylene terpolymers, and the like. As an example,an olefin copolymer, such as an ethylene copolymer, can be derived fromethylene and a comonomer, such as 1-butene, 1-hexene, or 1-octene. Ifthe monomer and comonomer were ethylene and 1-hexene, respectively, theresulting polymer can be categorized an as ethylene/1-hexene copolymer.

In like manner, the scope of the term “polymerization” includeshomopolymerization, copolymerization, terpolymerization, etc. Therefore,a copolymerization process can involve contacting one olefin monomer(e.g., ethylene) and one olefin comonomer (e.g., 1-hexene) to produce acopolymer.

The term “co-catalyst” is used generally herein to refer to compoundssuch as aluminoxane compounds, organoboron or organoborate compounds,ionizing ionic compounds, organoaluminum compounds, organozinccompounds, organomagnesium compounds, organolithium compounds, and thelike, that can constitute one component of a catalyst composition, whenused, for example, in addition to a fluorided silica-coated alumina. Theterm “co-catalyst” is used regardless of the actual function of thecompound or any chemical mechanism by which the compound may operate.

The terms “catalyst composition,” “catalyst mixture,” “catalyst system,”and the like, do not depend upon the actual product or compositionresulting from the contact or reaction of the initial components of thedisclosed or claimed catalyst composition/mixture/system, the nature ofthe active catalytic sites, or the fate of the co-catalyst, themagnesium compound, the titanium and/or vanadium component, or thefluorided silica-coated alumina, after combining these components.Therefore, the terms “catalyst composition,” “catalyst mixture,”“catalyst system,” and the like, encompass the initial startingcomponents of the composition, as well as whatever product(s) may resultfrom contacting these initial starting components, and this is inclusiveof both heterogeneous and homogenous catalyst systems or compositions.The terms “catalyst composition,” “catalyst mixture,” “catalyst system,”and the like, may be used interchangeably throughout this disclosure.

The term “contact product” is used herein to describe compositionswherein the components are contacted together in any order, in anymanner, and for any length of time, unless otherwise specified. Forexample, the components can be contacted by blending or mixing. Further,contacting of any component can occur in the presence or absence of anyother component of the compositions described herein. Combiningadditional materials or components can be done by any suitable method.Further, the term “contact product” includes mixtures, blends,solutions, slurries, reaction products, and the like, or combinationsthereof. Although “contact product” can include reaction products, it isnot required for the respective components to react with one another.Similarly, the term “contacting” is used herein to refer to materialswhich can be blended, mixed, slurried, dissolved, reacted, treated, orotherwise contacted in some other manner.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices, and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention.

Applicants disclose several types of ranges in the present invention.When Applicants disclose or claim a range of any type, Applicants'intent is to disclose or claim individually each possible number thatsuch a range could reasonably encompass, including end points of therange as well as any sub-ranges and combinations of sub-rangesencompassed therein. For example, when the Applicants disclose or claima chemical moiety having a certain number of carbon atoms, Applicants'intent is to disclose or claim individually every possible number thatsuch a range could encompass, consistent with the disclosure herein. Forexample, the disclosure that a moiety is a C₁ to C₁₈ hydrocarbyl group,or in alternative language, a hydrocarbyl group having from 1 to 18carbon atoms, as used herein, refers to a moiety that can have 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, aswell as any range between these two numbers (for example, a C₁ to C₈hydrocarbyl group), and also including any combination of ranges betweenthese two numbers (for example, a C₂ to C₄ and a C₁₂ to C₁₆ hydrocarbylgroup).

Similarly, another representative example follows for the ratio of Mw/Mnof an olefin polymer produced in an aspect of this invention. By adisclosure that the Mw/Mn can be in a range from about 2 to about 10,Applicants intend to recite that the Mw/Mn can be any ratio in the rangeand, for example, can be equal to about 2, about 3, about 4, about 5,about 6, about 7, about 8, about 9, or about 10. Additionally, the Mw/Mncan be within any range from about 2 to about 10 (for example, fromabout 3.5 to about 5.5), and this also includes any combination ofranges between about 2 and about 10 (for example, the Mw/Mn can be in arange from about 3 to about 6, or from about 7 to about 9). Likewise,all other ranges disclosed herein should be interpreted in a mannersimilar to these examples.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group, including any sub-ranges or combinations ofsub-ranges within the group, that can be claimed according to a range orin any similar manner, if for any reason Applicants choose to claim lessthan the full measure of the disclosure, for example, to account for areference that Applicants may be unaware of at the time of the filing ofthe application. Further, Applicants reserve the right to proviso out orexclude any individual substituents, analogs, compounds, ligands,structures, or groups thereof, or any members of a claimed group, if forany reason Applicants choose to claim less than the full measure of thedisclosure, for example, to account for a reference that Applicants maybe unaware of at the time of the filing of the application.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed generally to new catalystcompositions, methods for preparing catalyst compositions, methods forusing the catalyst compositions to polymerize olefins, the polymerresins produced using such catalyst compositions, and articles producedusing these polymer resins. In particular, the present invention relatesto catalyst compositions containing supported catalysts containing afluorided silica-coated alumina, a magnesium compound, and titanium (IV)and/or vanadium, to polymerization processes utilizing such catalystcompositions, and to the resulting olefin polymers produced from thepolymerization processes.

Fluorided Silica-Coated Aluminas

Fluorided silica-coated aluminas suitable for use in the presentinvention can include a silica-coated alumina treated with a variety offluorine-containing compounds or fluoriding sources. Illustrative andnon-limiting examples of fluorided silica-coated aluminas, silica-coatedaluminas, and fluorine-containing compounds are described in U.S. Pat.Nos. 7,884,163, 8,703,886, 8,916,494, and 9,023,959, which areincorporated herein by reference in their entirety.

The silica-coated alumina solid oxide materials which can be used canhave a silica content from about 5 to about 95% by weight. In oneaspect, the silica content of these solid oxides can be from about 10 toabout 80%, or from about 20% to about 70%, silica by weight. In anotheraspect, such materials can have silica contents ranging from about 15%to about 60%, or from about 25% to about 50%, silica by weight.Illustrative and non-limiting examples of silica-coated aluminamaterials suitable for use in this invention include Sasol SIRAL 28 (28%silica) and SIRAL 40 (40% silica), as well as those described in theexamples that follow. The silica-coated alumina solid oxides andfluorided silica-coated aluminas contemplated herein can have anysuitable surface area, pore volume, and particle size, as would berecognized by those of skill in the art.

The fluorided silica-coated alumina can be prepared by contacting asilica-coated alumina with a fluorine-containing compound and calcining.In some aspects, the silica-coated alumina and the fluorine-containingcompound can be contacted in the vapor phase, while in other aspects,the contacting of the silica-coated alumina and the fluorine-containingcompound can be conducted in the liquid phase. Moreover, the calciningcan be conducted after the silica-coated alumina and thefluorine-containing compound have been contacted, or the calcining canbe conducted concurrently with the contacting of the silica-coatedalumina and the fluorine-containing compound (e.g., in the vapor phase).

The calcining operation can be conducted at a variety of temperaturesand time periods, as described in the references noted herein.Additionally, the calcining operation can be performed in an ambientatmosphere (e.g., an oxidizing atmosphere), in a reducing atmosphere(e.g., containing molecular hydrogen and/or carbon monoxide, eitherindividually or in a mixture with an inert gas), or in an inertatmosphere (e.g., an inert gas such as nitrogen or argon).

The fluoride source or fluorine-containing compound, in certain aspects,can comprise a Freon or a fluorocarbon compound. For instance, suitablefluorine-containing compounds can include, but are not limited to,tetrafluoromethane, trifluoromethane, difluoromethane, fluoromethane,hexafluoroethane, pentafluoroethane, pentafluorodimethyl ether,1,1,2,2-tetrafluoroethane, 1,1,1,2-tetrafluoroethane,bis(difluoromethyl)ether, 1,1,2-trifluoroethane, 1,1,1-trifluoroethane,methyl trifluoromethyl ether, 2,2,2-trifluoroethyl methyl ether,1,2-difluoroethane, 1,1-difluoroethane, fluoroethane, octafluoropropane,1,1,2,2,3,3,3-heptafluoropropane, trifluoromethyl1,1,2,2-tetrafluoroethyl ether, 1,1,1,2,3,3,3-heptafluoropropane,trifluoromethyl 1,2,2,2-tetrafluoroethyl ether,1,1,1,2,2,3-hexafluoropropane, 1,1,1,2,3,3-hexafluoropropane,1,1,1,3,3,3-hexafluoropropane, 1,2,2,2-tetrafluoroethyl difluoromethylether, hexafluoropropane, pentafluoropropane,1,1,2,2,3-pentafluoropropane, 1,1,2,3,3-pentafluoropropane,1,1,1,2,3-pentafluoropropane, 1,1,1,3,3-pentafluoropropane, methylpentafluoroethyl ether, difluoromethyl 2,2,2-trifluoroethyl ether,difluoromethyl 1,1,2-trifluoroethyl ether, 1,1,2,2-tetrafluoropropane,methyl 1,1,2,2-tetrafluoroethyl ether, trifluoropropane,difluoropropane, fluoropropane, octafluorocyclobutane, decafluorobutane,1,1,1,2,2,3,3,4,4-nonafluorobutane, 1,1,1,2,3,4,4,4-octafluorobutane,1,1,1,2,2,3,3-heptafluorobutane, perfluoropropyl methyl ether,perfluoroisopropyl methyl ether, 1,1,1,3,3-pentafluorobutane,perfluorohexane (tetradecafluorohexane), tetrafluoroethylene,1,1-difluoroethylene, fluoroethylene, hexafluoropropylene,2,3,3,3-tetrafluoropropene, hexafluoropropene trimer, and the like, aswell as combinations thereof.

In another aspect, the fluorine-containing compound can comprise (orconsist essentially of, or consist of) tetrafluoromethane,trifluoromethane, difluoromethane, fluoromethane, hexafluoroethane,pentafluoroethane, tetrafluoroethane, trifluoroethane, difluorethane,octafluoropropane, perfluorohexane, perfluorobenzene,pentafluorodimethyl ether, bis(difluoromethyl)ether, methyltrifluoromethyl ether, trifluoroethyl methyl ether, perfluoroaceticanhydride, trifluoroethanol, silicon tetrafluoride (SiF₄), hydrogenfluoride (HF), fluorine gas (F₂), boron trifluoride (BF₃), triflic acid,tetrafluoroboric acid, antimony pentafluoride, phosphorouspentafluoride, tin tetrafluoride, thionyl fluoride, or sulfurhexafluoride, and the like, as well as mixtures or combinations thereof.For instance, the fluorine-containing compound can comprise (or consistessentially of, or consist of) tetrafluoromethane; alternatively,trifluoromethane; alternatively, difluoromethane; alternatively,fluoromethane; alternatively, hexafluoroethane; alternatively,pentafluoroethane; alternatively, tetrafluoroethane; alternatively,trifluoroethane; alternatively, difluorethane; alternatively,octafluoropropane; alternatively, perfluorohexane; alternatively,perfluorobenzene; alternatively, pentafluorodimethyl ether;alternatively, bis(difluoromethyl)ether; alternatively, methyltrifluoromethyl ether; alternatively, trifluoroethyl methyl ether;alternatively, perfluoroacetic anhydride; alternatively,trifluoroethanol; alternatively, silicon tetrafluoride; alternatively,hydrogen fluoride; or alternatively, fluorine gas.

In yet another aspect, the fluorine-containing compound can comprisetetrafluoroethane, perfluorohexane, perfluoroacetic anhydride, and thelike, or any combination thereof. In still another aspect, thefluorine-containing compound can comprise tetrafluoroethane, oralternatively, the fluorine-containing compound can compriseperfluorohexane.

In other aspects, the fluorine-containing compound can comprise hydrogenfluoride (HF), ammonium fluoride (NH₄F), ammonium bifluoride (NH₄HF₂),ammonium tetrafluoroborate (NH₄BF₄), ammonium silicofluoride(hexafluorosilicate) ((NH₄)₂SiF₆), ammonium hexafluorophosphate(NH₄PF₆), hexafluorotitanic acid (H₂TiF₆), ammonium hexafluorotitanicacid ((NH₄)₂TiF₆), hexafluorozirconic acid (H₂ZrF₆), AlF₃, NH₄AlF₄,triflic acid, ammonium triflate, and the like, as well as mixtures orcombinations thereof. Hence, the fluorine-containing compound cancomprise (or consist essentially of, or consist of) hydrogen fluoride(HF); alternatively, ammonium fluoride (NH₄F); alternatively, ammoniumbifluoride (NH₄HF₂); alternatively, ammonium tetrafluoroborate (NH₄BF₄);alternatively, ammonium silicofluoride (hexafluorosilicate)((NH₄)₂SiF₆); alternatively, ammonium hexafluorophosphate (NH₄PF₆);alternatively, hexafluorotitanic acid (H₂TiF₆); alternatively, ammoniumhexafluorotitanic acid ((NH₄)₂TiF₆); alternatively, hexafluorozirconicacid (H₂ZrF₆); alternatively, AlF₃; alternatively, NH₄AlF₄;alternatively, triflic acid; or alternatively, ammonium triflate.

In a “vapor” phase preparation, one or more of these fluorine-containingcompounds can be contacted with the silica-coated alumina during thecalcining operation; for example, a suitable fluorine-containingcompound can be vaporized into a gas stream used to fluidize thesilica-coated alumina during calcination. In another “vapor” phasepreparation, the silica-coated alumina can be exposed to a reactivefluoriding agent vapor at room temperature or slightly higher (e.g.,suitable fluorine-containing compounds include HF, BF₃, SiF₄, thionylfluoride, etc.), followed by subsequent calcining. In yet another“vapor” phase preparation, a suitable fluorine-containing compound(e.g., ammonium tetrafluoroborate, ammonium hexafluorosilicate, etc.)can be dry-mixed with the silica-coated alumina, and then heated todecompose the fluorine-containing compound, releasingfluorine-containing vapors, which react with the support. Thedecomposition and concurrent/subsequent calcining often can occur in the100° C. to 700° C. range, in the 150° C. to 700° C. range, and the like.In a “liquid” phase preparation, one or more of thesefluorine-containing compounds (e.g., ammonium tetrafluoroborate,ammonium hexafluorosilicate, ammonium bifluoride, hydrofluoric acid,triflic acid, etc.) can be mixed with a slurry of the silica-coatedalumina in a suitable solvent (e.g., water, C₁-C₃ alcohols, etc.),followed by (drying, if desired, and) subsequent calcining. Othersuitable procedures are well known to those of skill in the art.

The fluorided silica-coated alumina generally can contain from about 1to about 25 wt. % of fluorine (F), based on the weight of the fluoridedsilica-coated alumina. In particular aspects provided herein, thefluorided silica-coated alumina can contain from about 1 to about 20 wt.%, from about 2 to about 20 wt. %, from about 3 to about 20 wt. %, fromabout 2 to about 15 wt. %, from about 3 to about 15 wt. %, from about 3to about 12 wt. %, or from about 4 to about 10 wt. %, of fluorine, basedon the total weight of the fluorided silica-coated alumina.

Other suitable processes and procedures that may be applicable forpreparing fluorided silica-coated aluminas for use in the presentinvention can be found in U.S. Pat. Nos. 7,294,599, 7,601,665,7,884,163, 8,309,485, 8,623,973, 8,703,886, 8,916,494, and 9,023,959,which are incorporated herein by reference in their entirety.

Magnesium Compounds

Suitable magnesium compounds can include, but are not limited to,inorganic magnesium compounds, magnesium halides, magnesium alkoxides,alkoxymagnesium halides, and the like, as well as combinations thereof.For instance, the magnesium compound can comprise, either singly or incombination, MgCl₂, MgBr₂, MgI₂, MgSO₄, or Mg(NO₃)₂.

In an aspect, the magnesium compound can comprise a magnesium alkoxidecompound, and the magnesium alkoxide can have the formula, Mg(OR^(Z))₂.In this formula, each R^(Z) independently can be any C₁ to C₃₆ alkylgroup, C₁ to C₁₈ alkyl group, C₁ to C₁₂ alkyl group, C₁ to C₁₀ alkylgroup, or C₁ to C₆ alkyl group disclosed herein. Therefore, in someaspects, the alkyl group which can be R^(Z) can be a methyl group, anethyl group, a propyl group, a butyl group, a pentyl group, a hexylgroup, a heptyl group, an octyl group, a nonyl group, a decyl group, aundecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, apentadecyl group, a hexadecyl group, a heptadecyl group, or an octadecylgroup; or alternatively, a methyl group, an ethyl group, a propyl group,a butyl group, a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, or a decyl group. In some aspects, the alkyl groupwhich can be R^(Z) can be a methyl group, an ethyl group, a n-propylgroup, an iso-propyl group, a n-butyl group, an iso-butyl group, asec-butyl group, a tert-butyl group, a n-pentyl group, an iso-pentylgroup, a sec-pentyl group, or a neopentyl group; alternatively, a methylgroup, an ethyl group, an iso-propyl group, a tert-butyl group, or aneopentyl group; alternatively, a methyl group; alternatively, an ethylgroup; alternatively, a n-propyl group; alternatively, an iso-propylgroup; alternatively, a tert-butyl group; or alternatively, a neopentylgroup. In accordance with one aspect of this invention, each R^(Z) isdifferent, while in another aspect, both R^(Z) groups are the same. Inyet another aspect, the magnesium compound comprises magnesium methoxideand/or magnesium ethoxide; alternatively, magnesium methoxide; oralternatively, magnesium ethoxide.

Other magnesium compounds can be used, but in particular aspects of thisinvention, the magnesium compound is not a reducing agent, non-limitingexamples of which include magnesium hydrocarbyl compounds such asdibutyl magnesium, cyclopentadienyl magnesium, and the like; andGrignard reagents such as butyl magnesium bromide and the like.Accordingly, such compounds (e.g., magnesium hydrocarbyl compounds) arenot suitable for use as magnesium compounds in aspects of thisinvention.

Titanium (IV) and Vanadium Compounds

Suitable titanium (IV) compounds used in the processes for producing acatalyst disclosed herein (or suitable titanium (IV) species present onthe supported catalyst) can comprise titanium halides, titaniumalkoxides, alkoxytitanium halides, and the like, as well as combinationsthereof. For instance, the tetravalent titanium compound or species cancomprise, either singly or in combination, TiCl₄, TiBr₄, TiI₄, or TiF₄.

In an aspect, the tetravalent titanium compound or species can have theformula Ti(OR^(Z))_(n)X^(Z) _(4-n). In this formula, each R^(Z)independently can be any C₁ to C₃₆ alkyl group, C₁ to C₁₈ alkyl group,C₁ to C₁₂ alkyl group, C₁ to C₁₀ alkyl group, or C₁ to C₆ alkyl groupdisclosed herein, X^(Z) can be any suitable halogen, and n can be 0, 1,2, 3, or 4. Thus, suitable titanium (IV) compounds can include, but arenot limited to, TiCl₄, Ti(OR^(Z))Cl₃, Ti(OR^(Z))₂Cl₂, Ti(OR^(Z))₃Cl,where each R^(Z) independently can be a methyl group, an ethyl group, apropyl group, a butyl group, a pentyl group, a hexyl group, a heptylgroup, an octyl group, a nonyl group, a decyl group, a undecyl group, adodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group,a hexadecyl group, a heptadecyl group, or an octadecyl group; oralternatively, a methyl group, an ethyl group, a propyl group, a butylgroup, a pentyl group, a hexyl group, a heptyl group, an octyl group, anonyl group, or a decyl group. In accordance with one aspect of thisinvention, each R^(Z) is different, while in another aspect, each R^(Z)group is the same. In yet another aspect, the tetravalent titaniumcompound comprises TiCl₄.

Suitable vanadium compounds used in the processes for producing acatalyst disclosed herein (or suitable vanadium species present on thesupported catalyst) can comprise vanadium halides, vanadium alkoxides,alkoxyvanadium halides, and the like, as well as combinations thereof.For instance, the vanadium compound or species can comprise, eithersingly or in combination, VCl₃, VCl₄, or VOCl₃. The vanadium compound orspecies can have any suitable oxidation state, such as V(+3), V(+4), orV(+5).

In an aspect, the vanadium compound or species can have the formulaV(OR^(Z))_(n)X^(Z) _(4-n). In this formula, each R^(Z) independently canbe any C₁ to C₃₆ alkyl group, C₁ to C₁₈ alkyl group, C₁ to C₁₂ alkylgroup, C₁ to C₁₀ alkyl group, or C₁ to C₆ alkyl group disclosed herein,X^(Z) can be any suitable halogen, and n can be 0, 1, 2, 3, or 4. Thus,suitable vanadium compounds can include, but are not limited to, VCl₄,V(OR^(Z))Cl₃, V(OR^(Z))₂Cl₂, V(OR^(Z))₃Cl, where each R^(Z)independently can be a methyl group, an ethyl group, a propyl group, abutyl group, a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, a decyl group, a undecyl group, a dodecyl group, atridecyl group, a tetradecyl group, a pentadecyl group, a hexadecylgroup, a heptadecyl group, or an octadecyl group; or alternatively, amethyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group, ora decyl group. In accordance with one aspect of this invention, eachR^(Z) is different, while in another aspect, each R^(Z) group is thesame. In yet another aspect, the vanadium compound comprises VCl₃;alternatively, VCl₄; or alternatively, VOCl₃.

Supported Catalysts

Various processes for preparing supported catalysts for use in thepresent invention are disclosed and described herein. One such processcan comprise (or consist essentially of, or consist of) (i) contacting(a) a fluorided silica-coated alumina, (b) a magnesium compound, and (c)a first titanium (IV) compound and/or vanadium compound to form a firstsolid precatalyst; (ii) contacting the first solid precatalyst with anorganoaluminum compound to form a second solid precatalyst; and (iii)contacting the second solid precatalyst with a second titanium (IV)compound and/or vanadium compound to form the supported catalyst.

Generally, the features of any of the processes disclosed herein (e.g.,the fluorided silica-coated alumina, the magnesium compound, thetetravalent titanium compound, the vanadium compound, the organoaluminumcompound, the order of contacting, among others) are independentlydisclosed herein, and these features can be combined in any combinationto further describe the disclosed processes. Moreover, other processsteps can be conducted before, during, and/or after any of the stepslisted in the disclosed processes, unless stated otherwise.Additionally, any supported catalysts produced in accordance with thedisclosed processes are within the scope of this disclosure and areencompassed herein.

In step (i) of these processes, the fluorided silica-coated alumina, themagnesium compound, and the first titanium (IV) compound and/or vanadiumcompound can be contacted or combined in any order, and under anysuitable conditions, to form the first solid precatalyst. Thus, avariety of temperatures and time periods can be employed. For instance,the catalyst components can be contacted at a temperature in a rangefrom about 0° C. to about 100° C.; alternatively, from about 0° C. toabout 75° C.; alternatively, from about 10° C. to about 90° C.;alternatively, from about 20° C. to about 60° C.; alternatively, fromabout 20° C. to about 50° C.; alternatively, from about 15° C. to about45° C.; or alternatively, from about 20° C. to about 40° C. In these andother aspects, these temperature ranges also are meant to encompasscircumstances where the components are contacted at a series ofdifferent temperatures, instead of at a single fixed temperature,falling within the respective ranges. As an example, the initialcontacting of the components of the first solid precatalyst can beconducted at an elevated temperature, following by cooling to a lowertemperature for longer term storage of the first solid precatalyst.

The duration of the contacting of the components to form the first solidprecatalyst is not limited to any particular period of time. Hence, thisperiod of time can be, for example, from as little as 1-10 seconds to aslong as 24-48 hours, or more. The appropriate period of time can dependupon, for example, the contacting temperature, the respective amounts ofthe fluorided silica-coated alumina, the magnesium compound, and thefirst tetravalent titanium compound (and/or vanadium compound) to becontacted or combined, the presence of diluents, the degree of mixing,and considerations for long term storage, among other variables.Generally, however, the period of time for contacting can be at leastabout 5 sec, at least about 10 sec, at least about 30 sec, at leastabout 1 min, at least about 5 min, at least about 10 min, and so forth.Assuming the first solid precatalyst is not intended for long termstorage, which could extend for days or weeks, typical ranges for thecontacting time can include, but are not limited to, from about 1 sec toabout 48 hr, from about 5 sec to about 48 hr, from about 30 sec to about24 hr, from about 1 min to about 18 hr, from about 1 min to about 6 hr,from about 5 min to about 24 hr, or from about 1 hr to about 6 hr.

Often, the fluorided silica-coated alumina, the magnesium compound, andthe first titanium (IV) compound and/or vanadium compound can becontacted in a solvent. The solvent can comprise, for instance, anysuitable non-polar aliphatic hydrocarbon, aromatic hydrocarbon, orchlorinated hydrocarbon, and the like, or combinations thereof.Illustrative examples of non-polar aliphatic hydrocarbons can include,but are not limited to, alkanes such as cyclohexane, isobutane,n-butane, n-pentane, isopentane, neopentane, n-hexane, n-heptane, andthe like, or combinations thereof. Illustrative examples of aromatichydrocarbons can include, but are not limited to, toluene, benzene,xylene, and the like, or combinations thereof. Illustrative examples ofchlorinated hydrocarbons can include, but are not limited to,chlorobenzene and the like.

In alternate aspects, the solvent can comprise any suitable polaraprotic solvent and/or any suitable Lewis base. Illustrative examples ofsuch solvents can include, but are not limited to, ethers, pyridines,THF, substituted THF, dimethoxyethane, 1,4-dioxane, and the like, aswell as combinations thereof.

In one aspect, the first solid precatalyst can be prepared by firstcontacting the fluorided silica-coated alumina and the magnesiumcompound in a solvent to form a mixture (e.g., a slurry), and thencontacting the mixture with the first titanium (IV) compound and/orvanadium compound. In another aspect, the first solid precatalyst can beprepared by first contacting a mixture (e.g., a solution) of themagnesium compound and the first titanium (IV) compound and/or vanadiumcompound in a solvent, and then contacting the mixture with thefluorided silica-coated alumina. In yet another aspect, the first solidprecatalyst can be prepared by combining the fluorided silica-coatedalumina, the magnesium compound, and the first titanium (IV) compoundand/or vanadium compound substantially contemporaneously, and mixing toensure sufficient contacting of all components. For each of these ordersof addition, the fluorided silica-coated alumina can be present as aslurry or, alternatively, the fluorided silica-coated alumina can bepresent as a dry solid. Likewise, the magnesium compound and the firsttitanium (IV) compound and/or vanadium compound can be in any suitableform, e.g., a solution, a slurry, etc.

If desired, the processes used to produce the first solid precatalystcan further comprise a step of filtering, and/or a step of washing,and/or a step of drying (e.g., under reduced pressure) the productresulting from contacting the fluorided silica-coated alumina, themagnesium compound, and the first titanium (IV) compound and/or vanadiumcompound. Thus, a filtering step can be used, or a washing step can beused, or a drying step can be used, to form and/or isolate the firstsolid precatalyst. Alternatively, a filtering step, a washing step, anda drying step can be used to form and/or isolate the first solidprecatalyst. Other suitable separation or isolation techniques known tothose of skill in the art can be used to prepare the first solidprecatalyst in various forms, such as a free-flowing solid, if desired.

In step (ii) of the process to produce a supported catalyst, the firstsolid precatalyst can be contacted with an organoaluminum compound,under any suitable conditions, to form a second solid precatalyst. Aswith step (i), a variety of temperatures and time periods can beemployed. For instance, the first solid precatalyst and theorganoaluminum compound can be contacted at a temperature in a rangefrom about 0° C. to about 100° C.; alternatively, from about 0° C. toabout 75° C.; alternatively, from about 10° C. to about 90° C.;alternatively, from about 20° C. to about 60° C.; alternatively, fromabout 20° C. to about 50° C.; alternatively, from about 15° C. to about45° C.; or alternatively, from about 20° C. to about 40° C. In these andother aspects, these temperature ranges also are meant to encompasscircumstances where the first solid precatalyst and the organoaluminumcompound are contacted at a series of different temperatures, instead ofat a single fixed temperature, falling within the respective ranges. Asan example, the initial contacting of the components of the second solidprecatalyst can be conducted at an elevated temperature, following bycooling to a lower temperature for longer term storage of the secondsolid precatalyst.

The duration of the contacting of the components to form the secondsolid precatalyst is not limited to any particular period of time.Hence, this period of time can be, for example, from as little as 1-10seconds to as long as 24-48 hours, or more. The appropriate period oftime can depend upon, for example, the contacting temperature, therespective amounts of the first solid precatalyst and the organoaluminumcompound to be contacted or combined, the presence of diluents, thedegree of mixing, and considerations for long term storage, among othervariables. Generally, however, the period of time for contacting can beat least about 5 sec, at least about 10 sec, at least about 30 sec, atleast about 1 min, at least about 5 min, at least about 10 min, and soforth. Assuming the second solid precatalyst is not intended for longterm storage, which could extend for days or weeks, typical ranges forthe contacting time can include, but are not limited to, from about 1sec to about 48 hr, from about 5 sec to about 48 hr, from about 30 secto about 24 hr, from about 1 min to about 18 hr, from about 1 min toabout 6 hr, from about 5 min to about 24 hr, or from about 1 hr to about12 hr.

Although not limited thereto, step (ii) typically can be performed bycontacting a slurry of the first solid precatalyst (in any suitablenon-polar solvent or any non-polar solvent disclosed herein) with asolution of the organoaluminum compound (in any suitable non-polarsolvent or any non-polar solvent disclosed herein). The solvents usedfor the first solid precatalyst and the organoaluminum compound can bethe same or different.

Illustrative and non-limiting examples of suitable organoaluminumcompounds can include trimethylaluminum (TMA), triethylaluminum (TEA),tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA),triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum,diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminumchloride, and the like, or combinations thereof.

The relative amount of the first solid precatalyst versus the amount ofthe organoaluminum compound is not particularly limited. However, in anaspect of this invention, the ratio of moles of aluminum of theorganoaluminum compound to the weight of the first solid precatalyst canrange from about 0.0001 to about 0.005 moles Al per gram of the firstsolid precatalyst. In another aspect, the ratio can fall within a rangefrom about 0.0001 to about 0.002, from about 0.0002 to about 0.002, fromabout 0.0005 to about 0.002, or from about 0.0005 to about 0.001, molesAl per gram of the first solid precatalyst.

If desired, the processes used to produce the second solid precatalystcan further comprise a step of filtering, and/or a step of washing,and/or a step of drying (e.g., under reduced pressure) the productresulting from contacting the first solid precatalyst and theorganoaluminum compound (and any accompanying solvents that may bepresent). Thus, a filtering step can be used, or a washing step can beused, or a drying step can be used, to form and/or isolate the secondsolid precatalyst. Alternatively, a filtering step, a washing step, anda drying step can be used to form and/or isolate the second solidprecatalyst. Other suitable separation or isolation techniques known tothose of skill in the art can be used to prepare the second solidprecatalyst in various forms, such as a free-flowing solid, if desired.

In step (iii) of the process to produce a supported catalyst, the secondsolid precatalyst can be contacted with a second titanium (IV) compoundand/or vanadium compound, under suitable conditions, to form thesupported catalyst. The second titanium (IV) compound and/or vanadiumcompound can be the same as or different from the first titanium (IV)compound and/or vanadium compound. As with step (i) and step (ii), avariety of temperatures and time periods can be employed. For instance,the second solid precatalyst and the second titanium (IV) compoundand/or vanadium compound can be contacted at a temperature in a rangefrom about 0° C. to about 100° C.; alternatively, from about 0° C. toabout 75° C.; alternatively, from about 10° C. to about 90° C.;alternatively, from about 20° C. to about 60° C.; alternatively, fromabout 20° C. to about 50° C.; alternatively, from about 15° C. to about45° C.; or alternatively, from about 20° C. to about 40° C. In these andother aspects, these temperature ranges also are meant to encompasscircumstances where the second solid precatalyst and the second titanium(IV) compound and/or vanadium compound are contacted at a series ofdifferent temperatures, instead of at a single fixed temperature,falling within the respective ranges. As an example, the initialcontacting of the components of the supported catalyst can be conductedat an elevated temperature, following by cooling to a lower temperaturefor longer term storage of the supported catalyst.

The duration of the contacting of the components to form the supportedcatalyst is not limited to any particular period of time. Hence, thisperiod of time can be, for example, from as little as 1-10 seconds to aslong as 24-48 hours, or more. The appropriate period of time can dependupon, for example, the contacting temperature, the respective amounts ofthe second solid precatalyst and the second titanium (IV) compoundand/or vanadium compound to be contacted or combined, the presence ofdiluents, the degree of mixing, and considerations for long termstorage, among other variables. Generally, however, the period of timefor contacting can be at least about 5 sec, at least about 10 sec, atleast about 30 sec, at least about 1 min, at least about 5 min, at leastabout 10 min, and so forth. Assuming the supported catalyst is notintended for long term storage, which could extend for days or weeks,typical ranges for the contacting time can include, but are not limitedto, from about 1 sec to about 48 hr, from about 5 sec to about 48 hr,from about 30 sec to about 24 hr, from about 1 min to about 18 hr, fromabout 1 min to about 6 hr, from about 5 min to about 24 hr, or fromabout 1 hr to about 6 hr.

Although not limited thereto, step (iii) typically can be performed bycontacting a slurry of the second solid precatalyst (in any suitablenon-polar solvent or any non-polar solvent disclosed herein) with asolution of the second titanium (IV) compound and/or vanadium compound(in any suitable polar aprotic solvent or any polar aprotic solventdisclosed herein).

If desired, the processes used to produce the supported catalyst canfurther comprise a step of filtering, and/or a step of washing, and/or astep of drying (e.g., under reduced pressure) the product resulting fromcontacting the second solid precatalyst and the second titanium (IV)compound and/or vanadium compound (and any accompanying solvents thatmay be present). Thus, a filtering step can be used, or a washing stepcan be used, or a drying step can be used, to form and/or isolate thesupported catalyst. Alternatively, a filtering step, a washing step, anda drying step can be used to form and/or isolate the supported catalyst.Other suitable separation or isolation techniques known to those ofskill in the art can be used to prepare the supported catalyst invarious forms, such as a free-flowing solid, if desired.

In one aspect of the present invention, a supported titanium catalystcan be produced, and in this aspect, a titanium (IV) compound (one ormore) can be used in step (i) and step (iii), and the first titanium(IV) compound and the second titanium (IV) compound can be the same ordifferent. In another aspect, a supported vanadium catalyst can beproduced, and in this aspect, a vanadium compound (one or more) can beused in step (i) and step (iii), and the first vanadium compound and thesecond vanadium compound can be the same or different. In yet anotheraspect, a supported titanium and vanadium catalyst can be produced, andin this aspect, a first titanium (IV) compound can be used in step (i)and a second vanadium compound can be used in step (iii), or a firstvanadium compound can be used in step (i) and a second titanium (IV)compound can be used in step (iii).

In a related aspect, a supported catalyst consistent with this inventioncan comprise (or consist essentially of, or consist of) (a) a fluoridedsilica-coated alumina, (b) a magnesium compound, and (c) titanium (IV)and vanadium; alternatively, (a) a fluorided silica-coated alumina, (b)a magnesium compound, and (c) titanium (IV); or alternatively, (a) afluorided silica-coated alumina, (b) a magnesium compound, and (c)vanadium. In a further aspect, a supported catalyst consistent with thisinvention can comprise (or consist essentially of, or consist of) (a) afluorided silica-coated alumina, (b) a magnesium compound, and (c) atitanium (IV) compound and vanadium compound; alternatively, (a) afluorided silica-coated alumina, (b) a magnesium compound, and (c) atitanium (IV) compound; or alternatively, (a) a fluorided silica-coatedalumina, (b) a magnesium compound, and (c) a vanadium compound.

Consistent with aspects of this invention, the weight percentage ofmagnesium, based on the weight of the supported catalyst, often can bein a range from about 0.1 to about 10 wt. %. For example, the weightpercentage can be in a range from about 0.25 to about 10 wt. %magnesium, from about 0.25 to about 8 wt. % magnesium, or from about0.25 to about 5 wt. % magnesium. In specific aspects, the weightpercentage of magnesium, based on the weight of the supported catalyst,can be in a range from about 0.5 to about 7 wt. %, from about 0.5 toabout 5 wt. %, from about 0.5 to about 3 wt. %, from about 0.75 to about3 wt. %, or from about 0.75 to about 2 wt. % magnesium.

Additionally or alternatively, the weight percentage of titanium (orvanadium) of the tetravalent titanium compound (or of the vanadiumcompound), based on the weight of the supported catalyst, often can bein a range from about 0.1 to about 10 wt. %. For example, the weightpercentage can be in a range from about 0.1 to about 8 wt. %, from about0.1 to about 5 wt. %, or from about 0.1 to about 2 wt. % titanium (orvanadium). If both titanium and vanadium are present, this weightpercentage is based on the total of titanium and vanadium. In specificaspects, the weight percentage of titanium (or vanadium), based on theweight of the supported catalyst, can be in a range from about 0.2 toabout 7 wt. %, from about 0.2 to about 5 wt. %, from about 0.2 to about2 wt. %, from about 0.3 to about 2 wt. %, or from about 0.5 to about 2wt. % titanium (or vanadium).

In another aspect, the supported catalyst can further comprise a polaraprotic solvent, non-limiting examples of which can include ethers,pyridines, THF, substituted THF, dimethoxyethane, 1,4-dioxane, and thelike, as well as combinations thereof. This solvent can be coordinatedto the titanium (and/or vanadium) metal in the catalyst support, and isnot a free solvent. Often, the solvent can be present at an amount in arange from about 1 to about 500 ppm, or from about 1 to about 50 ppm,based on the weight of the supported catalyst. As an example, thesupported catalyst can further comprise THF at an amount in a range fromabout 1 to about 100 ppm, from about 1 to about 50 ppm, or from about 1to about 10 ppm.

In another aspect, the supported catalyst can further comprise anorganoaluminum compound and/or aluminum from the organoaluminumcompound. Often, the organoaluminum compound and/or aluminum from theorganoaluminum compound can be present at an amount in a range fromabout 1 to about 5000 ppm, from about 1 to about 1000 ppm, or from about1 to about 500 ppm, based on the weight of the supported catalyst.

Co-Catalysts

In certain aspects directed to catalyst compositions containing aco-catalyst, the co-catalyst can comprise a metal hydrocarbyl compound,examples of which include non-halide metal hydrocarbyl compounds, metalhydrocarbyl halide compounds, non-halide metal alkyl compounds, metalalkyl halide compounds, and so forth. The hydrocarbyl group (or alkylgroup) can be any hydrocarbyl (or alkyl) group disclosed herein.Moreover, in some aspects, the metal of the metal hydrocarbyl can be agroup 1, 2, 11, 12, 13, or 14 metal; alternatively, a group 13 or 14metal; or alternatively, a group 13 metal. Hence, in some aspects, themetal of the metal hydrocarbyl (non-halide metal hydrocarbyl or metalhydrocarbyl halide) can be lithium, sodium, potassium, rubidium, cesium,beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, boron,aluminum, or tin; alternatively, lithium, sodium, potassium, magnesium,calcium, zinc, boron, aluminum, or tin; alternatively, lithium, sodium,or potassium; alternatively, magnesium or calcium; alternatively,lithium; alternatively, sodium; alternatively, potassium; alternatively,magnesium; alternatively, calcium; alternatively, zinc; alternatively,boron; alternatively, aluminum; or alternatively, tin. In some aspects,the metal hydrocarbyl or metal alkyl, with or without a halide, cancomprise a lithium hydrocarbyl or alkyl, a magnesium hydrocarbyl oralkyl, a boron hydrocarbyl or alkyl, a zinc hydrocarbyl or alkyl, or analuminum hydrocarbyl or alkyl.

In particular aspects directed to catalyst compositions containing aco-catalyst (the catalyst composition contains a fluorided silica-coatedalumina), the co-catalyst can comprise an aluminoxane compound, anorganoboron or organoborate compound, an ionizing ionic compound, anorgano aluminum compound, an organozinc compound, an organomagnesiumcompound, or an organolithium compound, and this includes anycombinations of these materials. In one aspect, the co-catalyst cancomprise an organoaluminum compound. In another aspect, the co-catalystcan comprise an aluminoxane compound, an organoboron or organoboratecompound, an ionizing ionic compound, an organozinc compound, anorganomagnesium compound, an organolithium compound, or any combinationthereof. In yet another aspect, the co-catalyst can comprise analuminoxane compound; alternatively, an organoboron or organoboratecompound; alternatively, an ionizing ionic compound; alternatively, anorganozinc compound; alternatively, an organomagnesium compound; oralternatively, an organolithium compound.

Specific non-limiting examples of suitable organoaluminum compounds caninclude trimethylaluminum (TMA), triethylaluminum (TEA),tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA),triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum,diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminumchloride, and the like, or combinations thereof. Representative andnon-limiting examples of aluminoxanes include methylaluminoxane,modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane,iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane,sec-butylaluminoxane, iso-butylaluminoxane, 1-pentylaluminoxane,2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane,neopentylaluminoxane, and the like, or any combination thereof.Representative and non-limiting examples of organoboron/organoboratecompounds include N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate,tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron,and the like, or mixtures thereof.

Examples of ionizing ionic compounds can include, but are not limitedto, the following compounds: tri(n-butyl)ammoniumtetrakis(p-tolyl)borate, tri(n-butyl) ammonium tetrakis(m-tolyl)borate,tri(n-butyl)ammonium tetrakis(2,4-dimethylphenyl)borate,tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate,tri(n-butyl)ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,N,N-dimethylanilinium tetrakis(p-tolyl)borate, N,N-dimethylaniliniumtetrakis(m-tolyl)borate, N,N-dimethylaniliniumtetrakis(2,4-dimethylphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-dimethyl-phenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate,triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate,triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate,triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropyliumtetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropyliumtetrakis(2,4-dimethylphenyl)borate, tropyliumtetrakis(3,5-dimethylphenyl)borate, tropyliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropyliumtetrakis(pentafluorophenyl) borate, lithiumtetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithiumtetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithiumtetrakis(2,4-dimethylphenyl)borate, lithiumtetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodiumtetrakis(pentafluorophenyl)borate, sodium tetraphenylborate, sodiumtetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodiumtetrakis(2,4-dimethylphenyl)borate, sodiumtetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassiumtetrakis(pentafluorophenyl)borate, potassium tetraphenylborate,potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate,potassium tetrakis(2,4-dimethylphenyl)borate, potassiumtetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, lithiumtetrakis(pentafluorophenyl)aluminate, lithium tetraphenylaluminate,lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate,lithium tetrakis(2,4-dimethylphenyl)aluminate, lithiumtetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate,sodium tetrakis(pentafluorophenyl)aluminate, sodiumtetraphenylaluminate, sodium tetrakis(p-tolyl)aluminate, sodiumtetrakis(m-tolyl)aluminate, sodiumtetrakis(2,4-dimethylphenyl)aluminate, sodiumtetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate,potassium tetrakis(pentafluorophenyl)aluminate, potassiumtetraphenylaluminate, potassium tetrakis(p-tolyl)aluminate, potassiumtetrakis(m-tolyl)aluminate, potassiumtetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate, and thelike, or combinations thereof.

Exemplary organozinc compounds which can be used as co-catalysts caninclude, but are not limited to, dimethylzinc, diethylzinc,dipropylzinc, dibutylzinc, dineopentylzinc, di(trimethylsilyl)zinc,di(triethylsilyl)zinc, di(triisoproplysilyl)zinc,di(triphenylsilyl)zinc, di(allyldimethylsilyl)zinc,di(trimethylsilylmethyl)zinc, and the like, or combinations thereof.

Similarly, exemplary organomagnesium compounds can include, but are notlimited to, dimethylmagnesium, diethylmagnesium, dipropylmagnesium,dibutylmagnesium, dineopentylmagnesium,di(trimethylsilylmethyl)magnesium, methylmagnesium chloride,ethylmagnesium chloride, propylmagnesium chloride, butylmagnesiumchloride, neopentylmagnesium chloride, trimethylsilylmethylmagnesiumchloride, methylmagnesium bromide, ethylmagnesium bromide,propylmagnesium bromide, butylmagnesium bromide, neopentylmagnesiumbromide, trimethylsilylmethylmagnesium bromide, methylmagnesium iodide,ethylmagnesium iodide, propylmagnesium iodide, butylmagnesium iodide,neopentylmagnesium iodide, trimethylsilylmethylmagnesium iodide,methylmagnesium ethoxide, ethylmagnesium ethoxide, propylmagnesiumethoxide, butylmagnesium ethoxide, neopentylmagnesium ethoxide,trimethylsilylmethylmagnesium ethoxide, methylmagnesium propoxide,ethylmagnesium propoxide, propylmagnesium propoxide, butylmagnesiumpropoxide, neopentylmagnesium propoxide, trimethylsilylmethylmagnesiumpropoxide, methylmagnesium phenoxide, ethylmagnesium phenoxide,propylmagnesium phenoxide, butylmagnesium phenoxide, neopentylmagnesiumphenoxide, trimethylsilylmethylmagnesium phenoxide, and the like, or anycombinations thereof.

Likewise, exemplary organolithium compounds can include, but are notlimited to, methyllithium, ethyllithium, propyllithium, butyllithium(e.g., t-butyllithium), neopentyllithium, trimethylsilylmethyllithium,phenyllithium, tolyllithium, xylyllithium, benzyllithium,(dimethylphenyl)methyllithium, allyllithium, and the like, orcombinations thereof.

Co-catalysts that can be used in the catalyst compositions of thisinvention are not limited to the co-catalysts described above. Othersuitable co-catalysts are well known to those of skill in the artincluding, for example, those disclosed in U.S. Pat. Nos. 3,242,099,4,794,096, 4,808,561, 5,576,259, 5,807,938, 5,919,983, 7,294,599,7,601,665, 7,884,163, 8,114,946, and 8,309,485, which are incorporatedherein by reference in their entirety.

Catalyst Compositions

Various processes for preparing catalyst compositions containing asupported Ziegler component are disclosed and described herein. One suchprocess for producing a catalyst composition can comprise (or consistessentially of, or consist of) (i) contacting a fluorided silica-coatedalumina, a magnesium compound, and (c) a first titanium (IV) compoundand/or vanadium compound to form a first solid precatalyst; (ii)contacting the first solid precatalyst with an organoaluminum compoundto form a second solid precatalyst; (iii) contacting the second solidprecatalyst with a second titanium (IV) compound and/or vanadiumcompound to form the supported catalyst; and (iv) contacting thesupported catalyst and a co-catalyst to form the catalyst composition.

Generally, the features of any of the processes disclosed herein (e.g.,the fluorided silica-coated alumina, the magnesium compound, the firstand second titanium (IV) compound and/or vanadium compound, thesupported catalyst, and the co-catalyst, among others) are independentlydisclosed herein, and these features can be combined in any combinationto further describe the disclosed processes. Suitable fluoridedsilica-coated aluminas, magnesium compounds, titanium (IV) compoundsand/or vanadium compounds, supported catalysts, and co-catalysts arediscussed hereinabove. Moreover, other process steps can be conductedbefore, during, and/or after any of the steps listed in the disclosedprocesses, unless stated otherwise. Additionally, catalyst compositionsproduced in accordance with the disclosed processes are within the scopeof this disclosure and are encompassed herein.

In related aspects, a catalyst composition consistent with thisinvention can comprise (1) a supported catalyst comprising (a) afluorided silica-coated alumina, (b) a magnesium compound, and (c)titanium (IV) and/or vanadium; and (2) a co-catalyst. In furtheraspects, a catalyst composition consistent with this invention cancomprise (1) a supported catalyst comprising (a) a fluoridedsilica-coated alumina, (b) a magnesium compound, and (c) a titanium (IV)compound and/or vanadium compound; and (2) a co-catalyst. These catalystcompositions can be utilized to produce polyolefins—homopolymers,copolymers, and the like—for a variety of end-use applications.

In these methods and catalyst compositions, the weight ratio of theco-catalyst to the supported catalyst can be in a range from about 10:1to about 1:1000. If more than one co-catalyst and/or more than onesupported catalyst are employed, this ratio is based on the total weightof each respective component. In another aspect, the weight ratio of theco-catalyst to the supported catalyst can be in a range from about 1:1to about 1:1000, from about 1:1 to about 1:750, from about 1:10 to about1:750, or from about 1:50 to about 1:600.

The catalyst composition, in certain aspects of this invention, issubstantially free of aluminoxanes, organoboron or organoboratecompounds, ionizing ionic compounds, and/or other similar materials;alternatively, substantially free of aluminoxanes; alternatively,substantially free or organoboron or organoborate compounds; oralternatively, substantially free of ionizing ionic compounds. In theseaspects, the catalyst composition has catalyst activity in the absenceof these additional materials. For example, a catalyst composition ofthe present invention can consist essentially of (1) a supportedcatalyst comprising (a) a fluorided silica-coated alumina, (b) amagnesium compound, and (c) titanium (IV) and/or vanadium; and (2) aco-catalyst, wherein no other materials are present in the catalystcomposition which would increase/decrease the activity of the catalystcomposition by more than about 10% from the catalyst activity of thecatalyst composition in the absence of said materials.

However, in other aspects of this invention, these co-catalysts can beemployed. For example, the co-catalyst used in the catalyst compositioncan comprise an aluminoxane compound, an organoboron or organoboratecompound, an ionizing ionic compound, an organoaluminum compound, anorganozinc compound, an organomagnesium compound, an organolithiumcompound, and the like, or any combination thereof.

Catalyst compositions of the present invention have unexpectedly highcatalyst activity. Generally, the catalyst compositions have a catalystactivity greater than about 2,000 grams of ethylene polymer(homopolymer, copolymer, etc., as the context requires) per gram of thesupported Ziegler-type catalyst (which includes the fluoridedsilica-coated alumina) per hour (abbreviated g/g/hr). In another aspect,the catalyst activity can be greater than about 2,250, greater thanabout 2,500, or greater than about 3,000 g/g/hr. In still anotheraspect, catalyst compositions of this invention can be characterized byhaving a catalyst activity greater than about 3,000, or greater thanabout 4,000 g/g/hr, and often can range up to 8,000-10,000 g/g/hr. Theseactivities are measured under slurry polymerization conditions, with atriisobutylaluminum co-catalyst, using isobutane as the diluent, at apolymerization temperature of 80° C. and a reactor pressure of about 260psig.

In further aspects, catalyst compositions—containing a co-catalyst and asupported catalyst containing fluorided silica-coated alumina, amagnesium compound, and titanium (IV) and/or vanadium—consistent withthis invention can have catalyst activities that are greater than thatof similar catalyst systems than do not contain fluorided silica-coatedalumina, such as analogous catalyst systems containing sulfated alumina,when tested under the same conditions. Thus, the only difference is thepresence of a chemically-treated solid oxide other than fluoridedsilica-coated alumina. Moreover, catalyst compositions of this inventioncan have catalyst activities that are greater than that of similarcatalyst systems that contain transition metals (like Zr or Cr) insteadof Ti or V, under the same testing conditions. Additionally, catalystcompositions of this invention can have catalyst activities that aregreater than that of similar catalyst systems that do not contain themagnesium compound, under the same testing conditions. Catalystactivities are measured under slurry polymerization conditions, with atriisobutylaluminum co-catalyst, using isobutane as the diluent, at apolymerization temperature of 80° C. and a reactor pressure of about 260psig.

Olefin Monomers

Unsaturated reactants that can be employed with catalyst compositionsand polymerization processes of this invention typically can includeolefin compounds having from 2 to 30 carbon atoms per molecule andhaving at least one olefinic double bond. This invention encompasseshomopolymerization processes using a single olefin such as ethylene orpropylene, as well as copolymerization, terpolymerization, etc.,reactions using an olefin monomer with at least one different olefiniccompound. For example, the resultant ethylene copolymers, terpolymers,etc., generally can contain a major amount of ethylene (>50 molepercent) and a minor amount of comonomer (<50 mole percent), though thisis not a requirement. Comonomers that can be copolymerized with ethyleneoften can have from 3 to 20 carbon atoms, or from 3 to 10 carbon atoms,in their molecular chain.

Acyclic, cyclic, polycyclic, terminal (a), internal, linear, branched,substituted, unsubstituted, functionalized, and non-functionalizedolefins can be employed in this invention. For example, typicalunsaturated compounds that can be polymerized with the catalystcompositions of this invention can include, but are not limited to,ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene,the four normal octenes (e.g., 1-octene), the four normal nonenes, thefive normal decenes, and the like, or mixtures of two or more of thesecompounds. Cyclic and bicyclic olefins, including but not limited to,cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like,also can be polymerized as described herein. Styrene can also beemployed as a monomer in the present invention. In an aspect, the olefinmonomer can comprise a C₂-C₂₀ olefin; alternatively, a C₂-C₂₀alpha-olefin; alternatively, a C₂-C₁₀ olefin; alternatively, a C₂-C₁₀alpha-olefin; alternatively, the olefin monomer can comprise ethylene;or alternatively, the olefin monomer can comprise propylene.

When a copolymer (or alternatively, a terpolymer) is desired, the olefinmonomer and the olefin comonomer independently can comprise, forexample, a C₂-C₂₀ alpha-olefin. In some aspects, the olefin monomer cancomprise ethylene or propylene, which is copolymerized with at least onecomonomer (e.g., a C₂-C₂₀ alpha-olefin, a C₃-C₂₀ alpha-olefin, etc.).According to one aspect of this invention, the olefin monomer used inthe polymerization process can comprise ethylene. In this aspect,examples of suitable olefin comonomers can include, but are not limitedto, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene,1-decene, styrene, and the like, or combinations thereof. According toanother aspect of the present invention, the olefin monomer can compriseethylene, and the comonomer can comprise a C₃-C₁₀ alpha-olefin;alternatively, the comonomer can comprise 1-butene, 1-pentene, 1-hexene,1-octene, 1-decene, styrene, or any combination thereof; alternatively,the comonomer can comprise 1-butene, 1-hexene, 1-octene, or anycombination thereof; alternatively, the comonomer can comprise 1-butene;alternatively, the comonomer can comprise 1-hexene; or alternatively,the comonomer can comprise 1-octene.

Generally, the amount of comonomer introduced into a polymerizationreactor system to produce a copolymer can be from about 0.01 to about 50weight percent of the comonomer based on the total weight of the monomerand comonomer. According to another aspect of the present invention, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.01 to about 40 weight percent comonomer based on thetotal weight of the monomer and comonomer. In still another aspect, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.1 to about 35 weight percent comonomer based on thetotal weight of the monomer and comonomer. Yet, in another aspect, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.5 to about 20 weight percent comonomer based on thetotal weight of the monomer and comonomer.

While not intending to be bound by this theory, where branched,substituted, or functionalized olefins are used as reactants, it isbelieved that a steric hindrance can impede and/or slow thepolymerization process. Thus, branched and/or cyclic portion(s) of theolefin removed somewhat from the carbon-carbon double bond would not beexpected to hinder the reaction in the way that the same olefinsubstituents situated more proximate to the carbon-carbon double bondmight.

According to one aspect of the present invention, at least onemonomer/reactant can be ethylene (or propylene), so the polymerizationreaction can be a homopolymerization involving only ethylene (orpropylene), or a copolymerization with a different acyclic, cyclic,terminal, internal, linear, branched, substituted, or unsubstitutedolefin. In addition, the catalyst compositions of this invention can beused in the polymerization of diolefin compounds including, but notlimited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene.

Polymerization Processes

Catalyst compositions of the present invention can be used to polymerizeolefins to form homopolymers, copolymers, terpolymers, and the like. Onesuch process for polymerizing olefins in the presence of a catalystcomposition of the present invention can comprise contacting thecatalyst composition with an olefin monomer and optionally an olefincomonomer (one or more) in a polymerization reactor system underpolymerization conditions to produce an olefin polymer, wherein thecatalyst composition can comprise any of the catalyst compositionsdescribed herein, and/or the catalyst composition can be produced by anyof the processes for preparing catalyst compositions described herein.For instance, the catalyst composition can comprise (1) a supportedcatalyst comprising (a) a fluorided silica-coated alumina, (b) amagnesium compound, and (c) titanium (IV) and/or vanadium (or a titanium(IV) compound and/or vanadium compound); and (2) a co-catalyst. Thecomponents of the catalyst compositions are described herein.

The catalyst compositions of the present invention are intended for anyolefin polymerization method using various types of polymerizationreactor systems and reactors. The polymerization reactor system caninclude any polymerization reactor capable of polymerizing olefinmonomers and comonomers (one or more than one comonomer) to producehomopolymers, copolymers, terpolymers, and the like. The various typesof reactors include those that can be referred to as a batch reactor,slurry reactor, gas-phase reactor, solution reactor, high pressurereactor, tubular reactor, autoclave reactor, and the like, orcombinations thereof. Suitable polymerization conditions are used forthe various reactor types. Gas phase reactors can comprise fluidized bedreactors or staged horizontal reactors. Slurry reactors can comprisevertical or horizontal loops. High pressure reactors can compriseautoclave or tubular reactors. Reactor types can include batch orcontinuous processes. Continuous processes can use intermittent orcontinuous product discharge. Processes can also include partial or fulldirect recycle of unreacted monomer, unreacted comonomer, and/ordiluent.

Polymerization reactor systems of the present invention can comprise onetype of reactor in a system or multiple reactors of the same ordifferent type (e.g., a single reactor, dual reactor, more than tworeactors). Production of polymers in multiple reactors can includeseveral stages in at least two separate polymerization reactorsinterconnected by a transfer device making it possible to transfer thepolymers resulting from the first polymerization reactor into the secondreactor. The desired polymerization conditions in one of the reactorscan be different from the operating conditions of the other reactor(s).Alternatively, polymerization in multiple reactors can include themanual transfer of polymer from one reactor to subsequent reactors forcontinued polymerization. Multiple reactor systems can include anycombination including, but not limited to, multiple loop reactors,multiple gas phase reactors, a combination of loop and gas phasereactors, multiple high pressure reactors, or a combination of highpressure with loop and/or gas phase reactors. The multiple reactors canbe operated in series, in parallel, or both. Accordingly, the presentinvention encompasses polymerization reactor systems comprising a singlereactor, comprising two reactors, and comprising more than two reactors.The polymerization reactor system can comprise a slurry reactor, agas-phase reactor, a solution reactor, in certain aspects of thisinvention, as well as multi-reactor combinations thereof.

According to one aspect of the invention, the polymerization reactorsystem can comprise at least one loop slurry reactor comprising verticalor horizontal loops. Monomer, diluent, catalyst, and comonomer can becontinuously fed to a loop reactor where polymerization occurs.Generally, continuous processes can comprise the continuous introductionof monomer/comonomer, a catalyst, and a diluent into a polymerizationreactor and the continuous removal from this reactor of a suspensioncomprising polymer particles and the diluent. Reactor effluent can beflashed to remove the solid polymer from the liquids that comprise thediluent, monomer and/or comonomer. Various technologies can be used forthis separation step including, but not limited to, flashing that caninclude any combination of heat addition and pressure reduction,separation by cyclonic action in either a cyclone or hydrocyclone, orseparation by centrifugation.

A typical slurry polymerization process (also known as the particle formprocess) is disclosed, for example, in U.S. Pat. Nos. 3,248,179,4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, and 6,833,415,each of which is incorporated herein by reference in its entirety.

Suitable diluents used in slurry polymerization include, but are notlimited to, the monomer being polymerized and hydrocarbons that areliquids under polymerization conditions. Examples of suitable diluentsinclude, but are not limited to, hydrocarbons such as propane,cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, andn-hexane. Some loop polymerization reactions can occur under bulkconditions where no diluent is used.

According to yet another aspect of this invention, the polymerizationreactor system can comprise at least one gas phase reactor. Such systemscan employ a continuous recycle stream containing one or more monomerscontinuously cycled through a fluidized bed in the presence of thecatalyst under polymerization conditions. A recycle stream can bewithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product can be withdrawn from the reactor andnew or fresh monomer can be added to replace the polymerized monomer.Such gas phase reactors can comprise a process for multi-step gas-phasepolymerization of olefins, in which olefins are polymerized in thegaseous phase in at least two independent gas-phase polymerization zoneswhile feeding a catalyst-containing polymer formed in a firstpolymerization zone to a second polymerization zone. One type of gasphase reactor is disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790, and5,436,304, each of which is incorporated by reference in its entiretyherein.

According to still another aspect of the invention, a high pressurepolymerization reactor can comprise a tubular reactor or an autoclavereactor. Tubular reactors can have several zones where fresh monomer,initiators, or catalysts are added. Monomer can be entrained in an inertgaseous stream and introduced at one zone of the reactor. Initiators,catalysts, and/or catalyst components can be entrained in a gaseousstream and introduced at another zone of the reactor. The gas streamscan be intermixed for polymerization. Heat and pressure can be employedappropriately to obtain optimal polymerization reaction conditions.

According to yet another aspect of the invention, the polymerizationreactor system can comprise a solution polymerization reactor whereinthe monomer (and comonomer, if used) are contacted with the catalystcomposition by suitable stirring or other means. A carrier comprising aninert organic diluent or excess monomer can be employed. If desired, themonomer/comonomer can be brought in the vapor phase into contact withthe catalytic reaction product, in the presence or absence of liquidmaterial. The polymerization zone is maintained at temperatures andpressures that will result in the formation of a solution of the polymerin a reaction medium. Agitation can be employed to obtain bettertemperature control and to maintain uniform polymerization mixturesthroughout the polymerization zone. Adequate means are utilized fordissipating the exothermic heat of polymerization.

Polymerization reactor systems suitable for the present invention canfurther comprise any combination of at least one raw material feedsystem, at least one feed system for catalyst or catalyst components,and/or at least one polymer recovery system. Suitable reactor systemsfor the present invention can further comprise systems for feedstockpurification, catalyst storage and preparation, extrusion, reactorcooling, polymer recovery, fractionation, recycle, storage, loadout,laboratory analysis, and process control.

Polymerization conditions that are controlled for efficiency and toprovide desired polymer properties can include temperature, pressure,and the concentrations of various reactants. Polymerization temperaturecan affect catalyst productivity, polymer molecular weight, andmolecular weight distribution. A suitable polymerization temperature canbe any temperature below the de-polymerization temperature according tothe Gibbs Free energy equation. Typically, this includes from about 60°C. to about 280° C., for example, or from about 60° C. to about 120° C.,depending upon the type of polymerization reactor(s). In some reactorsystems, the polymerization temperature generally can fall within arange from about 70° C. to about 100° C., or from about 75° C. to about95° C. Various polymerization conditions can be held substantiallyconstant, for example, for the production of a particular grade ofolefin polymer.

Suitable pressures will also vary according to the reactor andpolymerization type. The pressure for liquid phase polymerizations in aloop reactor is typically less than 1000 psig (6.9 MPa). Pressure forgas phase polymerization is usually at about 200 to 500 psig (1.4 MPa to3.4 MPa). High pressure polymerization in tubular or autoclave reactorsis generally run at about 20,000 to 75,000 psig (138 to 517 MPa).Polymerization reactors can also be operated in a supercritical regionoccurring at generally higher temperatures and pressures. Operationabove the critical point of a pressure/temperature diagram(supercritical phase) may offer advantages.

Aspects of this invention are directed to olefin polymerizationprocesses comprising contacting a catalyst composition with an olefinmonomer and an optional olefin comonomer under polymerization conditionsto produce an olefin polymer. The olefin polymer (e.g., an ethylenehomopolymer or copolymer) produced by the process can have any of thepolymer properties disclosed herein, for example, a melt index of lessthan or equal to about 5 g/10 min (or less than or equal to about 2.5g/10 min), and/or ratio of Mw/Mn in a range from about 3 to about 5.5(or from about 3.5 to about 4.5), and/or density in a range from about0.90 g/cm³ to about 0.96 g/cm³ (or from about 0.91 g/cm³ to about 0.945g/cm³), and/or a NDR in a range from about 400 to about 600% (or fromabout 425 to about 550%), and/or a substantially constant short chainbranch distribution (SCBD), and/or low levels of long chain branches(LCB).

Aspects of this invention also are directed to olefin polymerizationprocesses conducted in the absence of added hydrogen. An olefinpolymerization process of this invention can comprise contacting acatalyst composition (i.e., any catalyst composition disclosed herein)with an olefin monomer and optionally an olefin comonomer in apolymerization reactor system under polymerization conditions to producean olefin polymer, wherein the polymerization process is conducted inthe absence of added hydrogen (no hydrogen is added to thepolymerization reactor system). As one of ordinary skill in the artwould recognize, hydrogen can be generated in-situ by catalystcompositions in various olefin polymerization processes, and the amountgenerated can vary depending upon the specific catalyst componentsemployed, the type of polymerization process used, the polymerizationreaction conditions utilized, and so forth.

In other aspects, it may be desirable to conduct the polymerizationprocess in the presence of a certain amount of added hydrogen.Accordingly, an olefin polymerization process of this invention cancomprise contacting a catalyst composition (i.e., any catalystcomposition disclosed herein) with an olefin monomer and optionally anolefin comonomer in a polymerization reactor system under polymerizationconditions to produce an olefin polymer, wherein the polymerizationprocess is conducted in the presence of added hydrogen (hydrogen isadded to the polymerization reactor system). For example, the ratio ofhydrogen to the olefin monomer in the polymerization process can becontrolled, often by the feed ratio of hydrogen to the olefin monomerentering the reactor. The added hydrogen to olefin monomer ratio in theprocess can be controlled at a weight ratio which falls within a rangefrom about 25 ppm to about 1500 ppm, from about 50 to about 1000 ppm, orfrom about 100 ppm to about 750 ppm.

In some aspects of this invention, the feed or reactant ratio ofhydrogen to olefin monomer can be maintained substantially constantduring the polymerization run for a particular polymer grade. That is,the hydrogen:olefin monomer ratio can be selected at a particular ratiowithin a range from about 5 ppm up to about 1000 ppm or so, andmaintained at the ratio to within about +/−25% during the polymerizationrun. For instance, if the target ratio is 100 ppm, then maintaining thehydrogen:olefin monomer ratio substantially constant would entailmaintaining the feed ratio between about 75 ppm and about 125 ppm.Further, the addition of comonomer (or comonomers) can be, and generallyis, substantially constant throughout the polymerization run for aparticular polymer grade.

However, in other aspects, it is contemplated that monomer, comonomer(or comonomers), and/or hydrogen can be periodically pulsed to thereactor, for instance, in a manner similar to that employed in U.S. Pat.No. 5,739,220 and U.S. Patent Publication No. 2004/0059070, thedisclosures of which are incorporated herein by reference in theirentirety.

The concentration of the reactants entering the polymerization reactorsystem can be controlled to produce resins with certain physical andmechanical properties. The proposed end-use product that will be formedby the polymer resin and the method of forming that product ultimatelycan determine the desired polymer properties and attributes. Mechanicalproperties include tensile, flexural, impact, creep, stress relaxation,and hardness tests. Physical properties include density, molecularweight, molecular weight distribution, melting temperature, glasstransition temperature, temperature melt of crystallization, density,stereoregularity, crack growth, long chain branching, and rheologicalmeasurements.

This invention is also directed to, and encompasses, the polymers (e.g.,ethylene homopolymers and ethylene/α-olefin copolymers) produced by anyof the polymerization processes disclosed herein. Articles ofmanufacture can be formed from, and/or can comprise, the polymersproduced in accordance with this invention.

Polymers and Articles

Certain aspects of this invention are directed to olefin polymers, suchas ethylene copolymers, that have a substantially constant short chainbranch distribution (SCBD). This feature often can be referred to as aflat SCBD, or alternatively, as a uniform or homogeneous comonomerdistribution. Ethylene copolymers having a uniform comonomerdistribution can, for example, have less polymer swell and lesssolubility in solvents/diluents than copolymers with heterogeneous andnon-uniform comonomer distributions, and this can be advantageous inslurry polymerization processes, particularly for lower densitycopolymers. Olefin polymers described herein, in certain aspects, canhave a unique combination of a flat SCBD and a relatively broadmolecular weight distribution, and such polymers can be produced using asupported catalyst system as disclosed herein.

Generally, olefin polymers encompassed herein can include any polymerproduced from any olefin monomer and comonomer(s) described herein. Forexample, the olefin polymer can comprise an ethylene homopolymer, apropylene homopolymer, an ethylene copolymer (e.g., ethylene/α-olefin,ethylene/1-butene, ethylene/1-hexene, ethylene/1-octene, etc.), apropylene copolymer, an ethylene terpolymer, a propylene terpolymer, andthe like, including combinations thereof. In one aspect, the olefinpolymer can be an ethylene/1-butene copolymer, an ethylene/1-hexenecopolymer, or an ethylene/1-octene copolymer, while in another aspect,the olefin polymer can be an ethylene/1-hexene copolymer.

If the resultant polymer produced in accordance with the presentinvention is, for example, an ethylene polymer, its properties can becharacterized by various analytical techniques known and used in thepolyolefin industry. Articles of manufacture can be formed from, and/orcan comprise, the ethylene polymers of this invention, whose typicalproperties are provided below.

An illustrative and non-limiting example of an olefin polymer (e.g., anethylene copolymer) of the present invention can have a melt index ofless than or equal to about 5 g/10 min, a ratio of Mw/Mn in a range fromabout 3 to about 5.5, a density in a range from about 0.90 g/cm³ toabout 0.96 g/cm³, a NDR in a range from about 400 to about 600%, and asubstantially constant short chain branch distribution (SCBD). Anotherillustrative and non-limiting example of an olefin polymer (e.g., anethylene copolymer) of the present invention can have a melt index ofless than or equal to about 2.5 g/10 min, a ratio of Mw/Mn in a rangefrom about 3.5 to about 4.5, a density in a range from about 0.91 g/cm³to about 0.945 g/cm³, a NDR in a range from about 425 to about 550%, anda substantially constant short chain branch distribution (SCBD). Theseillustrative and non-limiting examples of olefin polymers consistentwith the present invention also can have any of the polymer propertieslisted below and in any combination.

Polymers of ethylene (homopolymers, copolymers, etc.) produced inaccordance with some aspects of this invention generally can have a meltindex (MI) from 0 to about 5 g/10 min. Melt indices in the range from 0to about 3, from 0 to about 2.5, from 0 to about 2, or from 0 to about 1g/10 min, are contemplated in other aspects of this invention. Forexample, a polymer of the present invention can have a MI in a rangefrom about 0.1 to about 2.5, or from about 0.2 to about 2 g/10 min.

Consistent with certain aspects of this invention, ethylene polymersdescribed herein can have a high load melt index (HLMI) in a range from0 to about 100, from 0 to about 75, from 0 to about 50, or from about 5to about 100 g/10 min. In further aspects, ethylene polymers describedherein can have a HLMI in a range from about 5 to about 75, from about10 to about 100, or from about 10 to about 75 g/10 min.

The densities of ethylene-based polymers (e.g., ethylene homopolymers,ethylene copolymers) produced using the catalyst systems and processesdisclosed herein often are less than or equal to about 0.96 g/cm³, forexample, less than or equal to about 0.945 g/cm³, and often can rangedown to about 0.895 g/cm³. Yet, in particular aspects, the density canbe in a range from about 0.90 to about 0.96, such as, for example, fromabout 0.90 to about 0.95, from about 0.91 to about 0.945, from about0.91 to about 0.94, from about 0.92 to about 0.95, or from about 0.915to about 0.935 g/cm³.

Generally, polymers produced in aspects of the present invention areessentially linear or have very low levels of long chain branching, withtypically less than about 0.01 long chain branches (LCB) per 1000 totalcarbon atoms, and similar in LCB content to polymers shown, for example,in U.S. Pat. Nos. 7,517,939, 8,114,946, and 8,383,754, which areincorporated herein by reference in their entirety. In other aspects,the number of LCB per 1000 total carbon atoms can be less than about0.008, less than about 0.007, less than about 0.005, or less than about0.003 LCB per 1000 total carbon atoms.

In an aspect, ethylene polymers described herein can have a ratio ofMw/Mn, or the polydispersity index, in a range from about 2 to about 10,from about 3 to about 6, from about 3 to about 5.5, from about 3 toabout 5, or from about 3 to about 4.5. In another aspect, ethylenepolymers described herein can have a Mw/Mn in a range from about 3.5 toabout 6, from about 3.5 to about 5.5, from about 3.5 to about 5, or fromabout 3.5 to about 4.5.

In an aspect, ethylene polymers described herein can have a ratio ofMz/Mw in a range from about 2 to about 4, from about 2 to about 3.5,from about 2 to about 3.2, or from about 2 to about 3. In anotheraspect, ethylene polymers described herein can have a Mz/Mw in a rangefrom about 2.2 to about 3.5, from about 2.2 to about 3.2, from about 2.2to about 3, or from about 2.3 to about 2.9.

In an aspect, ethylene polymers described herein can have aweight-average molecular weight (Mw) in a range from about 80,000 toabout 650,000, from about 80,000 to about 550,000, from about 80,000 toabout 250,000, from about 80,000 to about 200,000, or from about 100,000to about 250,000 g/mol. Additionally or alternatively, ethylene polymersdescribed herein can have a number-average molecular weight (Mn) in arange from about 18,000 to about 150,000, from about 18,000 to about60,000, from about 20,000 to about 60,000, or from about 20,000 to about55,000 g/mol. Additionally or alternatively, ethylene polymers describedherein can have a z-average molecular weight (Mz) in a range from about200,000 to about 2,500,000, from about 200,000 to about 2,000,000, fromabout 200,000 to about 550,000, or from about 270,000 to about 500,000g/mol. Additionally or alternatively, ethylene polymers described hereincan have a unimodal molecular weight distribution, with a peak molecularweight (Mp) in a range from about 50,000 to about 500,000, from about50,000 to about 200,000, from about 50,000 to about 150,000, from about55,000 to about 125,000, or from about 60,000 to about 150,000 g/mol.

Ethylene copolymers, for example, produced using the polymerizationprocesses and catalyst systems described herein can, in some aspects,have a substantially constant SCBD. As noted above, this characteristicalso may be referred to as a flat or uniform SCBD or comonomerdistribution. In one aspect, the substantially constant SCBD can bedescribed by the slope of a plot of the number of short chain branchesper 1000 total carbon atoms versus the logarithm of molecular weight ofthe ethylene polymer (and determined via linear regression over therange from D15 to D85), and the slope can be in a range from about −0.6to about 0.6. In further aspects, the slope can be from about −0.5 toabout 0.5; alternatively, from about −0.4 to about 0.4; alternatively,from about −0.3 to about 0.3; or alternatively, from about −0.2 to about0.2. In another aspect, the substantially constant SCBD can be describedby the percentage of data points deviating from the average short chainbranch content of the polymer by greater than 0.5 short chain branchesper 1000 total carbon atoms (determined over the range from D15 to D85),and the percentage can be less than or equal to 20%. In further aspects,this percentage can be less than or equal to 15%; alternatively, lessthan or equal to 10%; or alternatively, less than or equal to 5%. In yetanother aspect, the substantially constant SCBD can be described by thepercentage of data points deviating from the average short chain branchcontent of the polymer by greater than 1 short chain branch per 1000total carbon atoms (determined over the range from D15 to D85), and thepercentage can be less than or equal to 15%. In further aspects, thispercentage can be less than or equal to 10%; alternatively, less than orequal to 3%; or alternatively, less than or equal to 1%.

D85 is the molecular weight at which 85% of the polymer by weight hashigher molecular weight, and D15 is the molecular weight at which 15% ofthe polymer by weight has higher molecular weight. Hence, thesubstantially constant, or flat, SCBD is determined over the D85 to D15molecular weight range.

In an aspect, ethylene polymers described herein can have a relativelylow natural draw ratio (NDR, %), often in a range from about 400 toabout 600%, from about 425 to about 600%, from about 400 to about 575%,from about 425 to about 575%, from about 425 to about 550%, or fromabout 450 to about 550%.

In an aspect, the olefin polymer described herein can be a reactorproduct (e.g., a single reactor product), for example, not apost-reactor blend of two or more polymers, for instance, havingdifferent molecular weight characteristics. As one of skill in the artwould readily recognize, physical blends of two or more differentpolymer resins can be made, but this necessitates additional processingand complexity not required for a reactor product.

Olefin polymers, whether homopolymers, copolymers, and so forth, can beformed into various articles of manufacture. Articles which can comprisepolymers of this invention include, but are not limited to, anagricultural film, an automobile part, a bottle, a container forchemicals, a drum, a fiber or fabric, a food packaging film orcontainer, a food service article, a fuel tank, a geomembrane, ahousehold container, a liner, a molded product, a medical device ormaterial, an outdoor storage product, outdoor play equipment, a pipe, asheet or tape, a toy, or a traffic barrier, and the like. Variousprocesses can be employed to form these articles. Non-limiting examplesof these processes include injection molding, blow molding, rotationalmolding, film extrusion, sheet extrusion, profile extrusion,thermoforming, and the like. Additionally, additives and modifiers areoften added to these polymers in order to provide beneficial polymerprocessing or end-use product attributes. Such processes and materialsare described in Modern Plastics Encyclopedia, Mid-November 1995 Issue,Vol. 72, No. 12; and Film Extrusion Manual—Process, Materials,Properties, TAPPI Press, 1992; the disclosures of which are incorporatedherein by reference in their entirety. In some aspects of thisinvention, an article of manufacture can comprise any of ethylenecopolymers described herein, and the article of manufacture can be afilm product or a molded product.

Applicants also contemplate a method for forming or preparing an articleof manufacture comprising a polymer produced by any of thepolymerization processes disclosed herein. For instance, a method cancomprise (i) contacting a catalyst composition with an olefin monomerand an optional olefin comonomer under polymerization conditions in apolymerization reactor system to produce an olefin polymer, wherein thecatalyst composition can comprise a supported catalyst and a co-catalyst(e.g., an organoaluminum compound); and (ii) forming an article ofmanufacture comprising the olefin polymer. The forming step can compriseblending, melt processing, extruding, molding, or thermoforming, and thelike, including combinations thereof.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

Melt index (MI, g/10 min) was determined in accordance with ASTM D1238at 190° C. with a 2,160 gram weight, and high load melt index (HLMI,g/10 min) was determined in accordance with ASTM D1238 at 190° C. with a21,600 gram weight. Polymer density was determined in grams per cubiccentimeter (g/cm³) on a compression molded sample, cooled at about 15°C. per hour, and conditioned for about 40 hours at room temperature inaccordance with ASTM D1505 and ASTM D4703. Natural Draw Ratio (NDR, %)was determined in accordance with ASTM D638 (see also U.S. Pat. No.7,589,162, which is incorporated herein by reference in its entirety).

Molecular weights and molecular weight distributions were obtained usinga PL-GPC 220 (Polymer Labs, an Agilent Company) system equipped with aIR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns(Waters, Mass.) running at 145° C. The flow rate of the mobile phase1,2,4-trichlorobenzene (TCB) containing 0.5 g/L2,6-di-t-butyl-4-methylphenol (BHT) was set at 1 mL/min, and polymersolution concentrations were in the range of 1.0-1.5 mg/mL, depending onthe molecular weight. Sample preparation was conducted at 150° C. fornominally 4 hr with occasional and gentle agitation, before thesolutions were transferred to sample vials for injection. An injectionvolume of about 400 μL was used. The integral calibration method wasused to deduce molecular weights and molecular weight distributionsusing a Chevron Phillips Chemical Company's HDPE polyethylene resin,MARLEX® BHB5003, as the broad standard. The integral table of the broadstandard was pre-determined in a separate experiment with SEC-MALS. Mnis the number-average molecular weight, Mw is the weight-averagemolecular weight, Mz is the z-average molecular weight, and Mp is thepeak molecular weight.

The long chain branches (LCB) per 1000 total carbon atoms can becalculated using the method of Janzen and Colby (J. Mol. Struct.,485/486, 569-584 (1999)), from values of zero shear viscosity, η_(o)(determined from the Carreau-Yasuda model), and measured values of Mwobtained using a Dawn EOS multiangle light scattering detector (Wyatt).See also U.S. Pat. No. 8,114,946; J. Phys. Chem. 1980, 84, 649; and Y.Yu, D. C. Rohlfing, G. R Hawley, and P. J. DesLauriers, PolymerPreprint, 44, 50, (2003). These references are incorporated herein byreference in their entirety.

Melt rheological characterizations were performed as follows.Small-strain (10%) oscillatory shear measurements were performed on aRheometrics Scientific, Inc. ARES rheometer using parallel-plategeometry. All rheological tests were performed at 190° C. The complexviscosity |η*| versus frequency (ω) data were then curve fitted usingthe modified three parameter Carreau-Yasuda (CY) empirical model toobtain the zero shear viscosity—η₀, characteristic viscous relaxationtime—τ_(η), and the breadth parameter—a. The simplified Carreau-Yasuda(CY) empirical model is as follows.

${{{\eta^{*}(\omega)}} = \frac{\eta_{0}}{\left\lbrack {1 + \left( {\tau_{\eta}\omega} \right)^{a}} \right\rbrack^{{({1 - n})}/a}}},$

wherein:

-   -   |η*(ω)|=magnitude of complex shear viscosity;    -   η₀=zero shear viscosity;    -   τ_(η)=viscous relaxation time (Tau(η));    -   a=“breadth” parameter (CY-a parameter);    -   n=fixes the final power law slope, fixed at 2/11; and    -   ω=angular frequency of oscillatory shearing deformation.

Details of the significance and interpretation of the CY model andderived parameters may be found in: C. A. Hieber and H. H. Chiang,Rheol. Acta, 28, 321 (1989); C. A. Hieber and H. H. Chiang, Polym. Eng.Sci., 32, 931 (1992); and R. B. Bird, R. C. Armstrong and O. Hasseger,Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition,John Wiley & Sons (1987); each of which is incorporated herein byreference in its entirety.

Short chain branch (SCB) content and short chain branching distribution(SCBD) across the molecular weight distribution were determined via anIR5-detected GPC system (IR5-GPC), wherein the GPC system was a PL220GPC/SEC system (Polymer Labs, an Agilent company) equipped with threeStyragel HMW-6E columns (Waters, Mass.) for polymer separation. Athermoelectric-cooled IR5 MCT detector (IR5) (Polymer Char, Spain) wasconnected to the GPC columns via a hot-transfer line. Chromatographicdata were obtained from two output ports of the IR5 detector. First, theanalog signal goes from the analog output port to a digitizer beforeconnecting to Computer “A” for molecular weight determinations via theCirrus software (Polymer Labs, now an Agilent Company) and the integralcalibration method using a broad MWD HDPE Marlex™ BHB5003 resin (ChevronPhillips Chemical) as the broad molecular weight standard. The digitalsignals, on the other hand, go via a USB cable directly to Computer “B”where they are collected by a LabView data collection software providedby Polymer Char. Chromatographic conditions were set as follows: columnoven temperature of 145° C.; flowrate of 1 mL/min; injection volume of0.4 mL; and polymer concentration of about 2 mg/mL, depending on samplemolecular weight. The temperatures for both the hot-transfer line andIR5 detector sample cell were set at 150° C., while the temperature ofthe electronics of the IR5 detector was set at 60° C. Short chainbranching content was determined via an in-house method using theintensity ratio of CH₃ (I_(CH3)) to CH₂ (I_(CH2)) coupled with acalibration curve. The calibration curve was a plot of SCB content(x_(SCB)) as a function of the intensity ratio of I_(CH3)/I_(CH2). Toobtain a calibration curve, a group of polyethylene resins (no less than5) of SCB level ranging from zero to ca. 32 SCB/1,000 total carbons (SCBStandards) were used. All these SCB Standards have known SCB levels andflat SCBD profiles pre-determined separately by NMR and thesolvent-gradient fractionation coupled with NMR (SGF-NMR) methods. UsingSCB calibration curves thus established, profiles of short chainbranching distribution across the molecular weight distribution wereobtained for resins fractionated by the IR5-GPC system under exactly thesame chromatographic conditions as for these SCB standards. Arelationship between the intensity ratio and the elution volume wasconverted into SCB distribution as a function of MWD using apredetermined SCB calibration curve (i.e., intensity ratio ofI_(CH3)/I_(CH2) vs. SCB content) and MW calibration curve (i.e.,molecular weight vs. elution time) to convert the intensity ratio ofI_(CH3)/I_(CH2) and the elution time into SCB content and the molecularweight, respectively.

Fluorided silica-coated alumina activator-supports were prepared asfollows. Bohemite was obtained from W.R. Grace & Company under thedesignation “Alumina A” and having a surface area of about 300 m²/g, apore volume of about 1.3 mL/g, and an average particle size of about 100microns. The alumina was first calcined in dry air at about 600° C. forapproximately 6 hours, cooled to ambient temperature, and then contactedwith tetraethylorthosilicate in isopropanol to equal 25 wt. % SiO₂.After drying, the silica-coated alumina was calcined at 600° C. for 3hours. Fluorided silica-coated alumina (7 wt. % F) was prepared byimpregnating the calcined silica-coated alumina with an ammoniumbifluoride solution in methanol, drying, and then calcining for 3 hoursat 600° C. in dry air. Afterward, the fluorided silica-coated alumina(FSCA) was collected and stored under dry nitrogen, and was used withoutexposure to the atmosphere.

Examples 1-13

Supported Ziegler-type catalysts were prepared as follows. A solution ofTiCl₄ (0.2 g) and MgCl₂ (0.2 g) in THF was added to a slurry offluorided silica-coated alumina (2 g) in dry heptane at room temperatureThe resulting mixture was stirred at room temperature for three morehours. The first solid precatalyst was isolated by centrifuge and washedseveral times with heptane. The first solid precatalyst was thendispersed in heptane and 2 mL of a 1 M solution of TIBA(triisobutylaluminum) in heptane was added. The resulting mixture wasstirred at room temperature overnight, the solvent was removed, and thesecond solid precatalyst was washed several times with heptane. Thesecond solid precatalyst was dispersed in heptane and a solution ofTiCl₄ (0.1 g) in THF was added to the slurry, and the mixture wasstirred at room temperature for three hours. The final supportedcatalyst was obtained after excess solvent was removed, washing severaltimes with heptane, and drying.

The resulting supported catalyst contained fluorided silica-coatedalumina with approximately 2.5 wt. % Mg and 3.8 wt. % Ti. The transitionmetal compound (TiCl₄) was present on the supported catalyst. Thesupported catalyst also contained about 2-4 ppm THF (by weight). Thesupported catalyst also contained TIBA or aluminum from the TIBA.

Example 1 was produced using the following polymerization procedure. Thepolymerization run was conducted in a one-gallon stainless steelreactor, and isobutane (2 L) was used. Under isobutane purge, 1 mL of 20wt. % TIBA in heptane was charged to the reactor, followed by 0.1 g ofthe dry supported catalyst. The charge port to the reactor was closedand isobutane was added. Hydrogen was added from a 325 cc auxiliaryvessel and the pressure drop from 600 psig starting pressure was noted.

The contents of the reactor were stirred and heated to 70° C., and 100psig (ΔP) of hydrogen was added. At 75° C., ethylene was then introducedalong with 100 g of 1-hexene. Ethylene was fed continuously to thereactor to maintain the total pressure at 260 psig for the 30 min lengthof the polymerization run. The reactor was controlled at 80° C.throughout the polymerization run by an automated heating-coolingsystem. After venting of the reactor, purging, and cooling, theresulting polymer product was dried under reduced pressure. For Example1, the catalyst activity was 6.2 kg/g/hr (kg of polymer per gram ofsupported catalyst per hour).

Examples 2-12 were produced using substantially the same polymerizationprocedure described for Example 1, with the following differences. ForExample 2, 150 g of 1-hexene was added, and the catalyst activity was6.4 kg/g/hr. For Example 3, the procedure of Example 2 was repeatedexcept that 120 psig (ΔP) of hydrogen was added, and the catalystactivity was 5.4 kg/g/hr. For Example 4, the procedure of Example 3 wasrepeated except that 150 psig (ΔP) of hydrogen was added, and thecatalyst activity was 6 kg/g/hr. For Example 5, the procedure of Example3 was repeated except that 180 psig (ΔP) of hydrogen was added, and thecatalyst activity was 4.6 kg/g/hr. For Example 6, the procedure ofExample 5 was repeated except that only 0.06 g of dry supported catalystwas added, and the catalyst activity was 4 kg/g/hr. For Example 7, theprocedure of Example 3 was repeated except that 160 psig (ΔP) ofhydrogen was added, and the catalyst activity was 3.3 kg/g/hr. ForExample 8, the procedure of Example 3 was repeated except that 140 psig(ΔP) of hydrogen was added, and the catalyst activity was 5.3 kg/g/hr.For Example 9, the procedure of Example 3 was repeated except that 170psig (ΔP) of hydrogen was added, and the catalyst activity was 6.4kg/g/hr. For Example 10, the procedure of Example 9 was repeated exceptthat 200 g of 1-hexene was added, and the catalyst activity was 4.3kg/g/hr. For Example 11, the procedure of Example 9 was repeated exceptthat 250 g of 1-hexene was added, and the catalyst activity was 4.8kg/g/hr. For Example 12, the procedure of Example 9 was repeated exceptthat 300 g of 1-hexene was added, and the catalyst activity was 3.6kg/g/hr.

Table I summarizes the melt index, high load melt index, density,zero-shear viscosity, and molecular weight parameters for the polymersof Examples 1-12, and demonstrates that a wide range of polymermolecular weights can be produced with the supported Ziegler-typecatalysts described herein. FIG. 1 illustrates the unimodal molecularweight distributions (amount of polymer versus molecular weight) for thepolymers of Examples 1 and 4-6, while FIG. 2 illustrates the unimodalmolecular weight distributions for the polymers of Examples 7-8 and10-11. Likewise, FIG. 5 illustrates the dynamic rheology properties at190° C. for the polymers of Examples 1 and 4-6, while FIG. 6 illustratesthe dynamic rheology properties at 190° C. for the polymers of Examples7-8 and 10-11. The Carreau-Yasuda (CY) model was used for therheological characterizations.

Although not tested, it was expected that the polymers of Examples 1-12would have low levels of long chain branches (LCB), with typically lessthan 0.008 LCB per 1000 total carbon atoms.

The unimodal molecular weight distribution and unexpected substantiallyconstant SCBD of the polymers produced using catalyst compositionsdisclosed herein—which contain a supported Ziegler-type catalyst usingfluorided silica-coated alumina—are illustrated in FIG. 3 for thepolymer of Example 10. This flat SCBD stands in contrast to that ofpolymers produced using conventional Ziegler-Natta catalysts, asdemonstrated in FIG. 4, where the flat SCBD of Example 10 is drasticallydifferent from the SCBD of Comparative Example 13 (produced using theprocedure of Example 1, except a conventional Ziegler-Natta catalyst wasused). Comparative Example 13 utilized Ziegler-Natta catalyst K, whichcontained about 14-19 wt. % titanium compounds (TiCl₃/TiCl₄), about17-24 wt. % MgCl₂, about 9-13 wt. % aluminum compounds, about 43-53 wt.% polyethylene, and less than about 3 wt. % heptane; the overall metalconcentration for Ti was in the 3.5-5.9 wt. % range, and for Mg was inthe 4.1-5.8 wt. % range. Comparative Example 13 illustrates aconventional SCBD in which the number of SCB's generally decreases asmolecular weight increases.

The polymer of Example 1 (1.97 MI, 0.9351 density) had a NDR of 486%,while the polymer of Comparative Example 13 (2.12 MI, 0.9346 density)had a NDR of 655%. This demonstrates the superior NDR performance forthe polymers produced using the catalyst systems described herein, ascompared to polymers produced using conventional Ziegler-Nattacatalysts: significantly lower NDR values, despite a slightly higherdensity. Lower NDR values typically correlate with improved stress crackresistance of the polymer, as well as with other beneficial polymerproperties.

TABLE I Examples 1-12. Mn/1000 Mw/1000 Mz/1000 Mp/1000 Density MI HLMIη_(o) Example (g/mol) (g/mol) (g/mol) (g/mol) Mw/Mn (g/cc) (g/10 min)(g/10 min0 (Pa-sec) 1 48 178 466 108 3.7 0.9351 1.97 55 3.55E+04 2 46176 427 111 3.8 0.9315 2.10 64 3.97E+04 3 45 174 447 102 3.9 0.9357 0.169 2.90E+04 4 36 136 378 74 3.8 0.9324 0.35 26 1.05E+04 5 25 101 271 614.0 0.9325 2.06 68 3.88E+03 6 27 121 331 73 4.5 0.9319 0.94 32 1.08E+047 38 140 367 83 3.7 0.9323 0.67 24 1.09E+04 8 39 151 382 85 3.9 0.93190.50 17 1.73E+04 9 102 539 1732 414 5.3 0.9253 — — 1.99E+06 10 31 121320 76 3.8 0.9354 1.38 42 6.87E+03 11 36 148 386 92 4.1 0.9303 0.47 201.54E+04 12 36 143 389 80 4.0 0.9300 0.68 25 1.10E+04

The invention is described above with reference to numerous aspects andembodiments, and specific examples. Many variations will suggestthemselves to those skilled in the art in light of the above detaileddescription. All such obvious variations are within the full intendedscope of the appended claims. Other embodiments of the invention caninclude, but are not limited to, the following (embodiments aredescribed as “comprising” but, alternatively, can “consist essentiallyof” or “consist of”):

Embodiment 1

A process to produce a supported catalyst, the process comprising:

(i) contacting:

-   -   (a) a fluorided silica-coated alumina;    -   (b) a magnesium compound; and    -   (c) a first titanium (IV) compound and/or vanadium compound to        form a first solid precatalyst;

(ii) contacting the first solid precatalyst with an organoaluminumcompound to form a second solid precatalyst; and

(iii) contacting the second solid precatalyst with a second titanium(IV) compound and/or vanadium compound to form the supported catalyst.

Embodiment 2

The process defined in embodiment 1, wherein step (i) comprisescontacting the fluorided silica-coated alumina with a mixture (e.g., asolution) of the magnesium compound and the first titanium (IV) compoundand/or vanadium compound.

Embodiment 3

The process defined in embodiment 1, wherein step (i) comprisescontacting the fluorided silica-coated alumina with a solution of themagnesium compound and the first titanium (IV) compound and/or vanadiumcompound in any suitable non-polar solvent or any non-polar solventdisclosed herein, e.g., aromatic hydrocarbons (e.g., toluene), alkanes(e.g., heptane), chlorinated hydrocarbons (e.g., chlorobenzene), etc.,as well as combinations thereof.

Embodiment 4

The process defined in embodiment 1, wherein step (i) comprisescontacting the fluorided silica-coated alumina with a solution of themagnesium compound and the first titanium (IV) compound and/or vanadiumcompound in any suitable polar aprotic solvent or any polar aproticsolvent disclosed herein, e.g., ethers, pyridines, THF, substituted THF,dimethoxyethane, 1,4-dioxane, etc., as well as combinations thereof.

Embodiment 5

The process defined in any one of the preceding embodiments, wherein instep (i), the fluorided silica-coated alumina is present as a slurry inany suitable non-polar solvent or any non-polar solvent disclosedherein, e.g., aromatic hydrocarbons (e.g., toluene), alkanes (e.g.,heptane), chlorinated hydrocarbons (e.g., chlorobenzene), etc., as wellas combinations thereof.

Embodiment 6

The process defined in any one of the preceding embodiments, wherein thecontacting in step (i) is conducted for any suitable time period or inany range of time periods disclosed herein, e.g., from about 5 secondsto about 48 hours, from about 1 minute to about 18 hours, from about 1to about 6 hours, etc.

Embodiment 7

The process defined in any one of the preceding embodiments, wherein thecontacting in step (i) is conducted at any suitable temperature or inany temperature range disclosed herein, e.g., from about 0° C. to about100° C., from about 10° C. to about 90° C., etc.

Embodiment 8

The process defined in any one of the preceding embodiments, whereinstep (i) further comprises filtering and/or washing and/or drying toisolate the first solid precatalyst.

Embodiment 9

The process defined in any one of the preceding embodiments, whereinstep (ii) comprises contacting a slurry of the first solid precatalyst(in any suitable non-polar solvent or any non-polar solvent disclosedherein) with a solution of the organoaluminum compound (in any suitablenon-polar solvent or any non-polar solvent disclosed herein), and thesolvents used for the first solid precatalyst and the organoaluminumcompound can be the same or different.

Embodiment 10

The process defined in any one of the preceding embodiments, wherein thecontacting in step (ii) is conducted for any suitable time period or inany range of time periods disclosed herein, e.g., from about 5 secondsto about 48 hours, from about 1 minute to about 18 hours, from about 1to about 12 hours, etc.

Embodiment 11

The process defined in any one of the preceding embodiments, wherein thecontacting in step (ii) is conducted at any suitable temperature or inany temperature range disclosed herein, e.g., from about 0° C. to about100° C., from about 10° C. to about 90° C., etc.

Embodiment 12

The process defined in any one of the preceding embodiments, whereinstep (ii) further comprises filtering and/or washing and/or drying toisolate the second solid precatalyst.

Embodiment 13

The process defined in any one of the preceding embodiments, whereinstep (iii) comprises contacting a slurry of the second solid precatalyst(in any suitable non-polar solvent or any non-polar solvent disclosedherein) with a solution of the second titanium (IV) compound and/orvanadium compound (in any suitable polar aprotic solvent or any polaraprotic solvent disclosed herein).

Embodiment 14

The process defined in any one of the preceding embodiments, wherein thecontacting in step (iii) is conducted for any suitable time period or inany range of time periods disclosed herein, e.g., from about 5 secondsto about 48 hours, from about 1 minute to about 18 hours, from about 1to about 6 hours, etc.

Embodiment 15

The process defined in any one of the preceding embodiments, wherein thecontacting in step (iii) is conducted at any suitable temperature or inany temperature range disclosed herein, e.g., from about 0° C. to about100° C., from about 10° C. to about 90° C., etc.

Embodiment 16

The process defined in any one of the preceding embodiments, whereinstep (iii) further comprises filtering and/or washing and/or drying toisolate the supported catalyst.

Embodiment 17

A supported catalyst produced by the process defined in any one of thepreceding embodiments.

Embodiment 18

A supported catalyst comprising:

-   -   (a) a fluorided silica-coated alumina;    -   (b) a magnesium compound; and    -   (c) titanium (IV) and/or vanadium.

Embodiment 19

The process or catalyst defined in any one of the preceding embodiments,wherein the fluorided silica-coated alumina comprises silica in anysuitable amount or in any range of weight percentages disclosed herein,e.g., from about 10 to about 80 wt. % silica, from about 20 to about 70wt. % silica, from about 25 to about 50 wt. % silica, etc., based on theweight of the fluorided silica-coated alumina.

Embodiment 20

The process or catalyst defined in any one of the preceding embodiments,wherein the weight percentage of F, based on the weight of the fluoridedsilica-coated alumina, is any suitable amount or in any range of weightpercentages disclosed herein, e.g., from about 1 to about 20 wt. %, fromabout 2 to about 15 wt. %, from about 3 to about 12 wt. %, etc.

Embodiment 21

The process or catalyst defined in any one of the preceding embodiments,wherein a weight percentage of magnesium, based on the weight of thesupported catalyst, is any suitable amount or in any weight percentagerange disclosed herein, e.g., from about 0.1 to about 10 wt. %, fromabout 0.25 to about 8 wt. %, from about 0.5 to about 7 wt. %, from about0.5 to about 3 wt. %, etc.

Embodiment 22

The process or catalyst defined in any one of the preceding embodiments,wherein a weight percentage of titanium (or vanadium), based on theweight of the supported catalyst, is any suitable amount or in anyweight percentage range disclosed herein, e.g., from about 0.1 to about10 wt. %, from about 0.2 to about 5 wt. %, from about 0.3 to about 2 wt.%, etc.

Embodiment 23

The process or catalyst defined in any one of embodiments 1-22, whereinthe magnesium compound comprises any suitable inorganic magnesiumcompound or any inorganic magnesium compound disclosed herein, e.g.,MgCl₂, MgBr₂, MgI₂, MgSO₄, Mg(NO₃)₂, etc., as well as combinationsthereof.

Embodiment 24

The process or catalyst defined in any one of embodiments 1-22, whereinthe magnesium compound comprises any suitable magnesium alkoxidecompound or any magnesium alkoxide compound disclosed herein, e.g.,magnesium methoxide, magnesium ethoxide, etc., as well as combinationsthereof.

Embodiment 25

The process or catalyst defined in any one of the preceding embodiments,wherein the magnesium compound comprises any suitable magnesium compoundthat is not a reducing agent (e.g., Grignard reagents such as butylmagnesium bromide; dibutyl magnesium; cyclopentadienyl magnesium, etc.).

Embodiment 26

The process or catalyst defined in any one of the preceding embodiments,wherein the titanium (IV) compound used in the process (or the titanium(IV) species present on the catalyst) comprises any suitable titaniumcompound or any titanium compound disclosed herein, e.g., TiCl₄, TiBr₄,TiI₄, TiF₄, titanium alkoxides, etc., as well as combinations thereof.

Embodiment 27

The process or catalyst defined in any one of the preceding embodiments,wherein the vanadium compound used in the process (or the vanadiumspecies present on the catalyst) comprises any suitable vanadiumcompound (e.g., V(III), V(IV), V(V)) or any vanadium compound disclosedherein, e.g., vanadium halides, VCl₃, VCl₄, VOCl₃, vanadium alkoxides,etc., as well as combinations thereof.

Embodiment 28

The process or catalyst defined in any one of the preceding embodiments,wherein the catalyst further comprises any suitable polar aproticsolvent or any polar aprotic solvent disclosed herein, e.g., ethers,pyridines, THF, substituted THF, dimethoxyethane, 1,4-dioxane, etc., aswell as combinations thereof, at an amount in any range disclosedherein, e.g., from about 1 to about 500 ppm, from about 1 to about 50ppm, from about 1 to about 10 ppm, etc., based on the weight of thesupported catalyst.

Embodiment 29

A catalyst composition comprising the supported catalyst defined in anyone of embodiments 17-28 and any suitable co-catalyst or any co-catalystdisclosed herein.

Embodiment 30

The composition defined in embodiment 29, wherein the catalystcomposition comprises an aluminoxane co-catalyst, an organoaluminumco-catalyst, an organoboron co-catalyst, or any combination thereof.

Embodiment 31

The composition defined in embodiment 29, wherein the catalystcomposition comprises an organoaluminum co-catalyst comprisingtrimethylaluminum, triethylaluminum, tri-n-propylaluminum,tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminumethoxide, diethylaluminum chloride, or any combination thereof.

Embodiment 32

The composition defined in any one of embodiments 29-31, wherein theweight ratio of the co-catalyst to the supported catalyst is anysuitable weight ratio or in any range disclosed herein, e.g., from about10:1 to about 1:1000, from about 1:1 to about 1:750, from about 1:50 toabout 1:600, etc.

Embodiment 33

The composition defined in any one of embodiments 25-28, wherein thecatalyst composition has a catalyst activity in any range of catalystactivities disclosed herein, e.g., greater than about 2,000 g/g/hr,greater than about 2,500 g/g/hr, greater than about 3,000 g/g/hr,greater than about 4,000 g/g/hr, etc.

Embodiment 34

The composition defined in any one of embodiments 29-33, wherein thecatalyst composition is substantially free of aluminoxane compounds,organoboron or organoborate compounds, ionizing ionic compounds, orcombinations thereof.

Embodiment 35

An olefin polymerization process, the process comprising contacting thecatalyst composition defined in any one of embodiments 29-34 with anolefin monomer and an optional olefin comonomer in a polymerizationreactor system under polymerization conditions to produce an olefinpolymer.

Embodiment 36

The process defined in embodiment 35, wherein the olefin monomercomprises any olefin monomer disclosed herein, e.g., any C₂-C₂₀ olefin.

Embodiment 37

The process defined in embodiment 35 or 36, wherein the olefin monomerand the optional olefin comonomer independently comprise a C₂-C₂₀alpha-olefin.

Embodiment 38

The process defined in any one of embodiments 35-37, wherein the olefinmonomer comprises ethylene.

Embodiment 39

The process defined in any one of embodiments 35-38, wherein thecatalyst composition is contacted with ethylene and an olefin comonomercomprising a C₃-C₁₀ alpha-olefin.

Embodiment 40

The process defined in any one of embodiments 35-39, wherein thecatalyst composition is contacted with ethylene and an olefin comonomercomprising 1-butene, 1-hexene, 1-octene, or a mixture thereof.

Embodiment 41

The process defined in any one of embodiments 35-37, wherein the olefinmonomer comprises propylene.

Embodiment 42

The process defined in any one of embodiments 35-41, wherein thepolymerization reactor system comprises a batch reactor, a slurryreactor, a gas-phase reactor, a solution reactor, a high pressurereactor, a tubular reactor, an autoclave reactor, or a combinationthereof.

Embodiment 43

The process defined in any one of embodiments 35-42, wherein thepolymerization reactor system comprises a slurry reactor, a gas-phasereactor, a solution reactor, or a combination thereof.

Embodiment 44

The process defined in any one of embodiments 35-43, wherein thepolymerization reactor system comprises a loop slurry reactor.

Embodiment 45

The process defined in any one of embodiments 35-44, wherein thepolymerization reactor system comprises a single reactor.

Embodiment 46

The process defined in any one of embodiments 35-44, wherein thepolymerization reactor system comprises 2 reactors.

Embodiment 47

The process defined in any one of embodiments 35-44, wherein thepolymerization reactor system comprises more than 2 reactors.

Embodiment 48

The process defined in any one of embodiments 35-47, wherein the olefinpolymer comprises any olefin polymer disclosed herein.

Embodiment 49

The process defined in any one of embodiments 35-40 and 42-48, whereinthe olefin polymer is an ethylene/1-butene copolymer, anethylene/1-hexene copolymer, or an ethylene/1-octene copolymer.

Embodiment 50

The process defined in any one of embodiments 35-40 and 42-48, whereinthe olefin polymer is an ethylene/1-hexene copolymer.

Embodiment 51

The process defined in any one of embodiments 35-37 and 41-48, whereinthe olefin polymer is a polypropylene homopolymer or a propylene-basedcopolymer.

Embodiment 52

The process defined in any one of embodiments 35-51, wherein thepolymerization conditions comprise a polymerization reaction temperaturein a range from about 60° C. to about 120° C. and a reaction pressure ina range from about 200 to about 1000 psig (about 1.4 to about 6.9 MPa).

Embodiment 53

The process defined in any one of embodiments 35-52, wherein thepolymerization conditions are substantially constant, e.g., for aparticular polymer grade.

Embodiment 54

The process defined in any one of embodiments 35-53, wherein no hydrogenis added to the polymerization reactor system.

Embodiment 55

The process defined in any one of embodiments 35-53, wherein hydrogen isadded to the polymerization reactor system.

Embodiment 56

The process defined in any one of embodiments 35-55, wherein the olefinpolymer is characterized by any MI disclosed herein, and/or any HLMIdisclosed herein, and/or any density disclosed herein, and/or any Mndisclosed herein, and/or any Mw disclosed herein, and/or any Mzdisclosed herein, and/or any Mw/Mn disclosed herein, and/or any Mz/Mwdisclosed herein.

Embodiment 57

The process defined in any one of embodiments 35-56, wherein the olefinpolymer has less than about 0.01 long chain branches (LCB) per 1000total carbon atoms, e.g., less than about 0.008 LCB, less than about0.005 LCB, etc.

Embodiment 58

The process defined in any one of embodiments 35-57, wherein the olefinpolymer has a flat or substantially constant short chain branchdistribution (SCBD), as determined by any procedure disclosed herein.

Embodiment 59

The process defined in any one of embodiments 35-58, wherein the olefinpolymer has a NDR in any range disclosed herein, e.g., from about 400 toabout 600%, from about 425 to about 550%, etc.

Embodiment 60

An olefin polymer produced by the polymerization process defined in anyone of embodiments 35-59.

Embodiment 61

An article comprising the olefin polymer defined in Embodiment 60.

Embodiment 62

A method or forming or preparing an article of manufacture comprising anolefin polymer, the method comprising (i) performing the olefinpolymerization process defined in any one of embodiments 35-59 toproduce the olefin polymer, and (ii) forming the article of manufacturecomprising the olefin polymer, e.g., via any technique disclosed herein.

Embodiment 63

The article defined in embodiment 61 or 62, wherein the article is anagricultural film, an automobile part, a bottle, a drum, a fiber orfabric, a food packaging film or container, a food service article, afuel tank, a geomembrane, a household container, a liner, a moldedproduct, a medical device or material, a pipe, a sheet or tape, or atoy.

We claim:
 1. A process to produce a supported catalyst, the processcomprising: (i) contacting: (a) a fluorided silica-coated alumina; (b) amagnesium compound; and (c) a first titanium (IV) compound and/orvanadium compound to form a first solid precatalyst; (ii) contacting thefirst solid precatalyst with an organoaluminum compound to form a secondsolid precatalyst; and (iii) contacting the second solid precatalystwith a second titanium (IV) compound and/or vanadium compound to formthe supported catalyst.
 2. The process of claim 1, wherein step (i)comprises contacting a slurry of the fluorided silica-coated alumina ina non-polar solvent with a solution of the magnesium compound and thefirst titanium (IV) compound and/or vanadium compound in a polar aproticsolvent.
 3. The process of claim 1, wherein step (ii) comprisescontacting a slurry of the first solid precatalyst with a solution ofthe organoaluminum compound.
 4. The process of claim 1, wherein step(iii) comprises contacting a slurry of the second solid precatalyst in anon-polar solvent with a solution of the second titanium (IV) compoundand/or vanadium compound in a polar aprotic solvent.
 5. The process ofclaim 1, wherein the fluorided silica-coated alumina comprises fromabout 20 to about 45 wt. % silica and from about 2 to about 15 wt. %fluorine.
 6. The process of claim 1, wherein the supported catalystcomprises from about 0.5 to about 7 wt. % magnesium.
 7. The process ofclaim 1, wherein the supported catalyst comprises from about 0.5 toabout 10 wt. % titanium.
 8. A catalyst composition comprising aco-catalyst and a supported catalyst comprising: (a) a fluoridedsilica-coated alumina; (b) a magnesium compound; and (c) titanium (IV)and/or vanadium.
 9. The composition of claim 8, wherein: the fluoridedsilica-coated alumina comprises from about 20 to about 45 wt. % silicaand from about 3 to about 12 wt. % fluorine; the supported catalystcomprises from about 0.5 to about 3 wt. % magnesium, and the magnesiumcompound is not a reducing agent; and the supported catalyst comprisesfrom about 0.5 to about 10 wt. % titanium.
 10. The composition of claim8, wherein the supported catalyst comprises a titanium (IV) compoundcomprising a titanium halide, a titanium alkoxide, an alkoxytitaniumhalide, or a combination thereof.
 11. The composition of claim 8,wherein the supported catalyst comprises a magnesium halide, a magnesiumalkoxide, an alkoxymagnesium halide, or a combination thereof.
 12. Thecomposition of claim 8, wherein the supported catalyst further comprisesfrom about 1 to about 50 ppm THF by weight.
 13. The composition of claim8, wherein a weight ratio of the co-catalyst to the supported catalystis in a range from about 1:50 to about 1:600.
 14. The composition ofclaim 8, wherein the catalyst composition has a catalyst activitygreater than about 2,000 g/g/hr, under slurry polymerization conditions,with a triisobutylaluminum co-catalyst, using isobutane as the diluent,at a polymerization temperature of 80° C. and a reactor pressure of 260psig.
 15. An olefin polymerization process, the process comprisingcontacting the catalyst composition of claim 8 with an olefin monomerand an optional olefin comonomer in a polymerization reactor systemunder polymerization conditions to produce an olefin polymer.
 16. Theprocess of claim 15, wherein the catalyst composition is contacted withethylene and an olefin comonomer comprising 1-butene, 1-hexene,1-octene, or a mixture thereof.
 17. The process of claim 15, wherein thepolymerization reactor system comprises a slurry reactor, a gas-phasereactor, a solution reactor, or a combination thereof.
 18. The processof claim 15, wherein the olefin polymer is an ethylene/alpha-olefincopolymer.
 19. The process of claim 18, wherein theethylene/alpha-olefin copolymer has less than about 0.008 long chainbranches per 1000 total carbon atoms and a substantially constant shortchain branch distribution (SCBD).
 20. The process of claim 18, whereinthe ethylene/alpha-olefin copolymer has a Natural Draw Ratio (NDR) in arange from about 400% to about 600%.